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X-ray structural studies of some group VIII compounds with catalytic implications

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Title:
X-ray structural studies of some group VIII compounds with catalytic implications
Added title page title:
X-ray structural studies of some group eight compounds with catalytic implications
Creator:
Sullivan, Douglas Allen, 1945- ( Dissertant )
Palenik, Gus J. ( Thesis advisor )
Stoufer, R. Carl ( Reviewer )
Ryschkewitsch, George E. ( Reviewer )
Helling, John P. ( Reviewer )
Renner, Richard ( Reviewer )
Place of Publication:
Gainesville, Fla.
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University of Florida
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Language:
English
Physical Description:
xiii, 237 leaves : ill. ; 28cm.

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Subjects / Keywords:
Atomic structure ( jstor )
Atoms ( jstor )
Clans ( jstor )
Cobalt ( jstor )
Crystal structure ( jstor )
Hydrogen ( jstor )
Ligands ( jstor )
Molecular structure ( jstor )
Molecules ( jstor )
Nickel ( jstor )
Chemistry thesis Ph. D ( local )
Dissertations, Academic -- Chemistry -- UF ( local )
Metals ( lcsh )
X-ray crystallography ( lcsh )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Abstract:
X-ray structural investigations of compounds containing Group VIII metal atoms are presented. The compounds studied illustrate interatomic interactions which may be of importance in catalytic processes. The structures of metal-containing compounds were solved by locating the heavy atoms in Patterson functions and locating the remaining atoms in Fourier syntheses. The direct method of symbolic addition was used in the one, all light-atom case presented. Trial structures were refined by the method of least-squares.The crystal structure of trans -chloro (dimethylglyoximato) (dimethylglyoxime) (4-chloroaniline) cobalt (III) illustrates an unusual ligand-induced proton shift. Both neutral and dianionic dimethylglyoxime groups are found in the complex and the 4-chloroaniline ligand is oriented over the dianionic dimethylglyoxime. The structure of trans-bis (dimethylxiglyoximato) bis (4-chloroaniline) cobalt (III) chloride shows that complex to contain two monoatomic dimethylglyoxime ligands and the 4-chloroaniline ligands to be skewed relative to the diglyoxime ligands. The crystal structure of trans-chlorobis (diphenylglyoximato) {4-chloroaniline) cobalt- (III) is described. Trends in the structures of these compounds and in the previously reported structures of similar compounds are discussed. Ultraviolet and infrared spectra of these compounds are given. The synthesis of a novel chelating ligand capable of binding two metal ions is described. The characterizations, including crystal structures, of its protonated forin, 1,4-dihydrazinophthalazinebis (2-pyridiniuracarboxaldimine) nitrate dihydrate, and of a nickel complex, y-chlorotetraaqua []. ,4- dihydrazinophthalazinebis (2-pyridinecarboxaldimine) ]dinickel- (II) chloride dihydrate, are presented. The planar ligand is shown to bind tv/o nickel ions with a separation of 3. COS o (1) A. A chloride ion occupies a bridging site in the plane of the nickel atoms and the ligand. The magnetic moment per nickel atom of the chloride bridged complex was deteinnined to be 2.74 B.M. at 40°C. The plausibility of structurally similar complexes mimicking the nitrogen-fixing enzyme nitrogenase is also discussed. The X-ray crystal structures of 1- (ir-cyclopentadienyl) - l-triphenylphosphine-2 ,3,4, 5-tetrakis (pentaf luorophenyl) cobaltole and 1- (Tr-cyclopentadienyl) -1-triphenylphosphine- 2 ,3, 4 , 5-tetrakis (pentaf luorophenyl) rhodole are reported. These compounds are viewed as stabilized intermediates in the catalyzed cyclization of acetylenes. In each case the metal atom forms a metallocyclo by a-bonding to the terminal carbons of a butadiene-like fragment. The ir-bonding in the metallocycle appears to be dclocalized.
Thesis:
Thesis--University of Florida.
Bibliography:
Bibliography: leaves 230-236.
Additional Physical Form:
Also available on World Wide Web
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Douglas Allen Sullivan.

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Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
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X-RAY STRUCTURAL STUDIES OF SOME GROUP VIII COMPOUNDS WITH CATALYTIC IMPLICATIONS By DOUGLAS ALLEN SULLIVAN A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 1975

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To Jeanie

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ACKNOWLEDGEMErJTS I sincerely thank Dr. Gus J. Palenik for his enthusiastic guidance throughout this work. I am deeply appreciative of the advice and instruction concerning crystallographic techniques given by Dr. M. Mathew and of the diligent synthetic work of Ruth C. Palenik. I wish to thank Dr. Marvin Rausch for providing excellent samples of metallocycle compounds. I am indebted to the chemistry faculties of Marshall University and the University of Florida for their apt instruction. I would like to especially thank the other members of the Center for Molecular Structure for their thoughtful suggestions and discussions. The typing expertise of Ann Kennedy is evident in this, perhaps her last, crystallographic dissertation. Lyle Plymale and Don Herbert are acknowledged for their inspirational teaching during my formative years. I would like to express my appreciation to my parents, Mr. and Mrs. I. O. Sullivan, for their support and encouragement throughout my formal education. Finally, I thank my wife, Jeanie, and my son, David, for their love and devoted understanding. Ill

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Table of Contents ACKNOWLEDGEMENTS LIST OF TABLES LIST OF FIGURES KEY TO ABBREVIATIONS ABSTRACT CHAPTER 1: CHAPTER 2: CHAPTER 3: CHAPTER 4: CHAPTER 5 CHAPTER 6 CHAPTER 7: INTRODUCTION SYNTHESES AND CHARACTERIZATION X-RAY DIFFRACTION EXPERIMENTAL AN INVESTIGATION OF LIGANDINDUCED PROTON SHIFT: THE CRYSTAL AND MOLECULAR STRUCTURES OF TRANS CHLORO (DIMETHYLGLYOXIMATO) (DIMETHYLGLYOXIME) (4-CHLOROANILINE) COBALT (III) DIHYDRATE, TRANS -CHLOROBIS (DIPHENYLGLY0XIJ4AT0) ( 4-CHLOROANILINE) COBALT ( III) ETHANOLATE, AND TRANS-B IS (DIMETHYLGLYOXIMATO) BIS (4-CHLOROANILINE) COBALT (III) CHLORIDE A NOVEL BINUCLEATING LIGAND: THE CRYSTAL AND MOLECULAR STRUCTURES OF 1,4-DIHYDPJ^ZINOPHTHALAZINEBIS (2-PYRIDINIUMCARBOXALDIMINE) NITRATE DIHYDRATE AND y-CHLOROTETRAAQUA [1 , 4-DIHYDRAZINOPHTHALAZINE3IS ( 2-PYRIDINECARBOXALDIMINE) ] DINICKEL(II) CHLORIDE DIHYDRATE MODELS OF PROPOSED INTERMEDIATES FOR THE CATALYZED CYCLIZATION OF ACETYLENES: THE CRYSTAL AND MOLECULAR STRUCTURES OF 1(tt-CYCLOPENTADIENYL) -1-TRIPHENYLPHOSPHINE-2, 3,4,5-TETRAKIS (PENTAFLUOROPHENYL) COBALTOLE and 1(tt-CYCLOPENTADIENYL) -1TRIPHENYLPHOSPHINE-2 ,3,4, 5-TETPAKIS (PENTAFLUOROPHENYL) RHODOLE CONCLUDING REM^FJCS 111 vi ix X xi 1 4 17 30 83 114 141 IV

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APPENDIX A: BOOTHITl 144 APPENDIX B: OBSERVED AND CALCULATED STRUCTURE FACTORS 154 REFERENCES 230 BIOGRAPHICAL SKETCH 237

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LIST OF TABLES Table 1. Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9. Table 10. Table 11. Table 12. Table 13. Table 14. Table 15. Table 16. Elemental Analysis Infrared Spectra Ultraviolet Spectra Crystallographic Data Schemes of Refinement Final Atomic Parameters of Nonhydrogen Atoms for C£Co{H2dmg) (dmg) (clan) Final Parameters for the Hydrogen Atoms for C£Co(n2dmg) (dmg) (clan) Final Atomic Parameters for the Nonhydrogen Attorns of C'tCo(H2dpg2) (clan) Final Parameters for Hydrogen Atoms for C£Co(H2dpg2) (clan) Final Atomic Parameters for Nonhydrogen Atoms of [Co(Hdmg) 2 (clan) 2]C-e Final Pararaeters for Hydrogen Atoms for [Co(Hdmg) 2 (clan) 2]C£ Selected Interatomic Distances in Some Cobaloxime Complexes Selected Interatomic Angles in Some Cobaloxime Complexes Deviations and Selected Lcastin C£Co(H2dmg) ( Deviations and Selected Leastin C£Co(H2dpg2) Deviations and Selected Leastin [Co (Hdmg) ~ (c Equations of Squares Planes dmg) (clan) Equations of Squares Planes (clan) Equations of Squares Planes Ian) 2]C£ 8 10 15 18 28 33 35 37 41 43 45 52 54 59 61 63 vx

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Table 17. Table 18. Hydrogen Bonds in Cobaloximes Dihedral Angles Formed by Selected Planes in Some Cobaloxime Complexes Table 19. A Summary of the Average Bond Distances in XYCo(H2dmg2) Complexes Bond Distances and Bond Angles of Coordinated 4-Chloroaniline Molecules Bond Distances, Bond Angles, and Least-Squares Planes of Phenyl Rings in C£Co (H2dpg2) (clan) Final Atomic Parameters of Nonhydrogen Atoms for H2dhphpy(N03)2'^H20 Final Parameters for the Hydrogen Atoms in H2dhphpy(N03)2-2H20 Final Atomic Parameters of Nonhydrogen Atoms for [Ni2C£ {H2O) 4 (dhphpy) I Cl^ • 2H2O Final Parameters for the Hydrogen Atoms in [HiyCl (H2O) 4 (dhphpy) ] Cl^ ' 2H2O Selected Interatomic Distances for H2dhphpy(N03) 2-2H20 and [Ni2C£ {H2O) 4 (dhphpy) ] Cl^ ' 2H2O Selected Angles in H2dhphpy(N02)2'2H20 Table 20. Table 21. Table 22. Table 23. Table 24. Table 25. Table 26. Table 27. Table 28. Table 29. Table 30. 2H2O Selected Angles in [Ni2C£ (H2O) 4 (dhphpy) ] Cl^ Hydrogen Bonds in Hodhphpy(N03) 2-2H20 and [Ni2C£ (H2O) ^ (dhphpy) ] Cl^ • 2H2O Deviations and Equations of Selected Least-Squares Planes in H2dhphpy (N03)2-2H20 and [Ui^Cl (HO) 4 (dhphpy) ] Cl^ • 2H2O 64 73 77 80 81 85 86 88 92 98 100 101 103 109 Vll

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Table 31 Table 32. Table 33 Table 34 Table 35. Table 36 Table 37 Table 38 Table B-1. Table B-3 Table B-4 Table B-5, Final Atomic Parameters for the Nonhydrogen Atoms in C4 (fph) 4C0 (cp) (tpp) and C4(fph)4Rh(cp) (tpp) Selected Bond Distances of C^(fph)^M(cp) (tpp) Selected Bond Angles of C^(fph)^M(cp) (tpp) Deviation from and Equations of Some Least-Squares Planes of C4 (fph) 4Co(cp) (tpp) and C4(fph)^Rh(cp) (tpp) Average C-F and C-C Distances for the Pentaf luorophenyl Groups in C^ (f ph) ^M (cp) (tpp) Bond Distances and Bond Angles of Pentaf luorophei^iyl Groups in C^(fph)^Co(cp) (tpp) Bond Distances and Bond Angles of Pentaf luorop};.enyl Groups in C^ {fph)^Rh(cp) (tpp) Bond Distances and Bond Angles of Triphenylphosphine in C^(fph)^M(cp) (tpp) Observed and Calculated Structure Factors for C£Co (H^dpg^) (clan) 119 Table B-2. Observed and Calculated Structure Factors for [Co(Hdrag) (clan) ]C£ Observed and Calculated Structure Factors for H-dhphpy (NO^) „ • 2H Observed and Calculated Structure Factors for [Ni„C£ (H^O) . (dhphpy) ] C£2*2H20 ^ Observed and Calculated Structure Factors for C , (f ph) .Rh (cp) (tpp) 128 129 130 133 134 136 138 156 173 181 190 205 vixi

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LIST OF FIGURES Figure 1. An ORTEP drawing of 47 C£Co(H2dmg) (dmg) (clan) •2H2O Figure 2. An ORTEP drawing of 49 C£Co(H2dpg2) (clan) •C2H3OH r: 51 Figure 3. " An ORTEP drawing of [Co (Hdmg) 2 (clan) 2KC Figure 4. A projected view along Co-N(l) 70 for CCCo(H2dmg) (dmg) (clan) Figure 5. A projected view along Co-N(l) 72 for (a) [Co(ndrag)2(clan) 2]C£ and (b) CCCo (H2dpg2) (clan) Figure 6. An ORTEP drawing of H2dhphpy (N03)2'H20 Figure 7. An ORTEP drawing of [Ni2C^ (}l20) 4 (dhphpy) ]C£32H2O A packing diagram of 1^^ H2dhphpy (NO3) 2-2K20 Figure 8, Figure 9. A packing diagram of [Ni2C£ (II2O) 4 (dhphpy) ] 0^3 • 2H2O Figure 10. An ORTEP drawing of C4(fph)4Co(cp) (tpp) 95 97 108 126 IX

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KEY TO ABBREVIATIONS LIPS ligand-induced proton shift H-dmg dimethylglyoxime dmg dimethylglyoxime dianion Hdmg ' dimethylglyoxime monoanion Hpdmgbis (dimethylglyoximate) with relative proton positions unspecified sulfa sulfanilamide dhph 1, 4-dihydrazinophthalazine dhphpy 1, 4-dihydrazinophthalazinebis (2pyridinecarboxaldimine) pyca 2-pyridinecarboxaldehyde clan 4-chloroaniline Hjdph diphenylglyoxime Hjmpg methylphenylglyoxime fph pentaf luorophenyl cp cyclopentadienyl anion tpp triphenylphosphine an aniline 4-FPYTSC 4-formylpyridinethiosemicarbazone

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Abstract of Dissertation Presented to the Graduate Council of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy X-RAY STRUCTURAL STUDIES OF SOME GROUP VIII COMPOUNDS WITH CATALYTIC IMPLICATIONS By Douglas Allen Sullivan December, 19 75 Chairman: Gus J. Palenik Major Department: Chemistry X-ray structural investigations of compounds containing Group VIII metal atoms are presented. The compounds studied illustrate interatomic interactions which may be of importance in catalytic processes. The structures of metal-containing compounds were solved by locating the heav;^' atoms in Patterson functions and locating the remaining atoms in Fourier syntheses. The direct method of symbolic addition was used in the one, all light-atom case presented. Trial structures were refined by the method of least-squares. The crystal structure of trans -chloro (dimethylglyoximato) (dimethylglyoxime) (4-chloroaniline) cobalt (III) illustrates an unusual ligand-induced proton shift. Both neutral and dianionic dimethylglyoxime groups are found in the complex and the 4-chloroaniline ligand is oriented over the dianionic dimethylglyoxime. The structure of trans -bis (dimethylxi

PAGE 12

glyoximato) bis (4-chloroaniline) cobalt (III) chloride shows that complex to contain two monoatomic dimethylglyoxime ligands and the 4-chloroaniline ligands to be skewed relative to the diglyoxime ligands. The crystal structure of trans -chlorobis (diphenylglyoximato) {4-chloroaniline) cobalt(III) is described. Trends in the structures of these compounds and in the previously reported structures of similar compounds are discussed. Ultraviolet and infrared spectra of these compounds are given. The synthesis of a novel chelating ligand capable of binding two metal ions is described. The characterizations, including crystal structures, of its protonated forin, 1,4dihydrazinophthalazinebis (2-pyridiniuracarboxaldimine) nitrate dihydrate, and of a nickel complex, y-chlorotetraaqua []. ,4dihydrazinophthalazinebis (2-pyridinecarboxaldimine) ]dinickel(II) chloride dihydrate, are presented. The planar ligand is shown to bind tv/o nickel ions with a separation of 3. COS o (1) A. A chloride ion occupies a bridging site in the plane of the nickel atoms and the ligand. The magnetic moment per nickel atom of the chloride bridged complex was deteinnined to be 2.74 B.M. at 40°C. The plausibility of structurally similar complexes mimicking the nitrogen-fixing enzyme nitrogenase is also discussed. The X-ray crystal structures of 1(ir-cyclopentadienyl) l-triphenylphosphine-2 ,3,4, 5-tetrakis (pentaf luorophenyl) cobaltole and 1(Tr-cyclopentadienyl) -1-triphenylphosphine2 ,3, 4 , 5-tetrakis (pentaf luorophenyl) rhodole are reported. xii

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These compounds are viewed as stabilized intermediates in the catalyzed cyclization of acetylenes. In each case the metal atom forms a metallocyclo by a-bonding to the terminal carbons of a butadiene-like fragment. The ir-bonding in the metallocycle appears to be dclocalized. XI 11

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CHAPTER 1 INTRODUCTION Western civilization has demonstrated the efficiencyoriented phenomenon of expending large amounts of energy to find ways of requiring less human energy. This is evident in the evolution from animal trails to freeways and from muscle to sophisticated, high-energy machinery. On the molecular scale the more efficient path io provided by catalysts. As alchemists searched for the "philosopher's stone" many chemists have been seeking catalysts. The application of catalysis is now advancing through the development of an understanding of the mechanisms of catalytic processes. Life processes are dependent upon chemical reactions controlled by enzymes. "It is not generally appreciated how little is understood about the mechanisms by which enzymes bring about their extraordinary and specific rate acceleration." Investigation of enzymes should not only be fundamental in the understanding and maintenance of life processes but also should contribute to developing more efficient industrial processes. Much of the investigation of enzymes has concerned the use of model compounds. "Model building and the application of material analogues are becoming increasingly important for the elucidation of fundamental problems of biochemical

PAGE 15

structure and reactivity."^ X-ray structural studies of enzyme models are important for the exploration of structureactivity relationships. Solid state studies of enzymmodel compounds are of particular relevance I ocauso of the high degree of order the macromolecular enzymes themselves possess. While electrostatic and hydrogen-bonding forces are usually considered the major binding forces in enzyme-substrate interactions, the strong charge-solvating and hydrogen-bonding ability of water tends to reduce the possibility of obtaining large binding energies from these forces. To explain the large binding energies found, "hydrophobic forces" are presumed to exiso in these intermolecular interacions in aqueous solution.^ The enthalpies of mixing of aromatic liquids with aliphatic liquids indicate that aromatic molecules prefer an aromatic environment. ' "Stacking interactions" involving the 7i-systems of aromatic groups within the enzyme's protein structure may account for part of the "hydrophobic forces" and contribute to the orientation of the enzymesubstrate interaction.^ The ligand-induced proton shift (LIPS) observed in ClCoiU^dx^g) (dmg) (sulfa) [the key to abbreviations is given on page xl is an indication of the importance of this TT-type interaction. A further examination of LIPS v. as undertaken and is presented in this work. The design of enzyme models is often based on sparse structural information about the prosthetic group of the enzyme. Efforts to miiTLic the nitrocen-f ixing enzyme nitrogenase

PAGE 16

have been concerned with the metal to nitrogen bond. The 6 7 probable binuclear nature of the enzyme's active site ' has largely been ignored. The structures of a novel binucleating ligand and its nickel (II) complex are presented here as a first step in the construction of a new generation of models for nitrogenase. When the mechanism of a chemical process is believed to be understood, stable compounds similar to the intermediates of the reaction may be prepared and examined to support the proposed mechanism. One proposed mechanism for the catalyzed cyclization of acetylenes v/ould have a fivemembered ring containing a metal atom and a cyclobutadiene 8— 1 3 fragment as one of the intermediates. The first structure of such a stabiliF.ed intermediate containing a cobalt atom and the structure of the rhodiv;m analog are presented in this study.

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CHAPTER 2 SYNTHESIS AND CHARACTERIZATION Synthes is Crystals of all cobaloxime compounds were generously provided by R. C. Palenik* and were used v.'ithout recrystallization. M. D. Rausch and R. H. Gastinger synthesized the 14 15 metallocycles containgmg cobalt and rhodium. They supplied well-formed crystals of those metallocycles for X-ray structural studies. Unless otherwise indicated all solvents were reagent grade and were used without further purification. All preparations were carried out in air. All melting points were taken on a Mel-temp apparatus in open capillaries and are uncorrected. 16 The published method was used to prepare dhph for succeeding experiments. To 6.40g (49.0 mmoles) 1,2-dicyanobenzene (98%; Aldrich Chemical Corripany, Milwaukee, Wise.) in 12.5 ml 1,4-dioxane was added a mixture of 15.0 ml (ca. 250 mmoles) hydrazine hydrate (85%; Fisher Scientific Company, Fair Lawn, N. Y.) and 4 . ml glacial acetic acid (reagent; Baker and Adamson, Morristown, N. J.). After being heated *These complexes were prepared using standard procedures with synthetic details to be published at a later date.

PAGE 18

for three hours the mixture was cooled and the red product was collected (yield, ca . 40%). The decomposition temperature of 193 °C was in agreement with the reported value. A solution of 0.0955g (0.50 mmoles) of the previously prepared dhph in 4 ml absolute ethanol was added to a solution of 0.237g (1.0 mmoles) UiCl2' ^^2^ (reagent; Matheson, Coleman and Bell, Norwood, Ohio) and 0.095 ml (0.99 mmoles) pyca (99%; Aldrich) in 40 ml absolute ethanol. Upon slow, almost complete, evaporation in air of that solution olive green crystals of [Ni2C£. (H2O) ^ (dhphpy) ] 0^3 • 2H2O formed. Analogous procedures were carried out replacing NiC£2 * H2O with CoCl2'^^-2^' CuC£2 '2^120 (reagent; Fisher), ZnCl2 (reagent; Mallinckrodt Chemical Works, St. Louis, Mo.) and FeC£2'4^2^ (reagent; r4atheson, Coleman and Bell) without success in obtaining a crystalline product. Similar procedures were followed with the addition of ca. 0.2 ml of 12 M hydrochloric acid (reagent, 38%; Baker and Adamson) to solutions of CuC£2'2H20 and FeCc2'4H20. Again, no suitable products were formed. Attempts to separate and recrystallize reaction products from water, water-ethanol , methanol and pyridine failed to give a crystalline product. V7hen CuC£2 was present, gas evolved from the reaction mixture. Additional attempts wore made to isolate complexes similar to {Ni C(l (H 0) (dhphpy) ] Ci^ using dhph obtained by recrystallization from hot water of H2dhphS0^ (ICN-K and K Laboratories, Ir>.c. , Plainviev/, N. Y.) to which an equivalent

PAGE 19

amount of KOH (certified A.C.S.; Fisher) had been added. Those attempts were unsuccessful. The red-orange plates of H2dhphpy (NO^) 2^ 2H2O used in crystallographic studies had been recrystallized from water. The crude product formed upon cooling a solution made by adding 0.190g (1.0 mmole) dhph in 20 ml warm water to a solution containing 0.583g (2.0 mmoles) Ni (NO-^) 2 ' ^H^O (reagent; Mallinckrodt) and 0.8 9 ml (9.4 mmoles) pyca in 10 ml warm water followed by drop-wise addition of nitric acid (reagent, 71%; Baker and Adamson) to a pH less than 1. Also, H^dhphpy (NO^) 2 was prepared by first adding 1.90 ml (20.0 miaoles) pyca to a suspension of 2.878g (10.0 mmoles) H2dhphS0. in 100 ml water. A brick-red solid formed upon addition of l.llg (ca. 17 mmoles) KOH. After washing with water and drying in air, the brick-red solid was suspended in 100 ml of 95% ethanol and 1.30 ml (21 mmoles) of nitric acid were added. Small red-orange needles of H2dhphpy (NO^) 2 which decompose at 126°C were filtered, v;ashed with ethanol, and then ether and air dried (yield 4.0g, 75%). Freshly prepared hydrated metal hydroxides were reacted with H2dhphpy (NO^) 2 in methanol. Each of the metal hydroxides was filtered after adding 1 M KOH to aqueous solutions of Ni(N02)2-6H20, Cu (NO^) 2 ' 3H2O (reagent; J. T. Baker Chemical Company, Phillipsburg, N. J.), Fe (C^O^) 2 • 6H2O (reagent; G. Frederick Smith Chemical Company, Columbus, Ohio) and Zn(NO,)2-6H (reagent; Matheson, Coleman and Bell). After

PAGE 20

the reaction mixtures were stirred until there was no further change in color, they were filtered and the filtrates were allowed to evaporate. Only the reaction with nickel (II) hydroxide produced a crystalline product. Attempts to recrystallize that maroon product from methanol, ethanol, ethanol-water, and 2-propanol did not yield crystals suitable for crystallographic studies. Discussion of Characterizatio n The microananlyses recorded in Table 1 were performed by Galbraith Laboratories, Inc., Knoxville, Tennessee, for the dhphpy compounds and by Atlantic Microlab, Inc., Atlanta, Georgia, for the cobaloxime complexes. The calculated percentages of carbon, hydrogen, and nitrogen for the dhphpy compounds correlate well with the measured percentage. Two water molecules per molecule of dhphpy in each are indicated by the elemental analysis. This is confirmed in the structural determination. Similarly, the eleraental analysis of C-tCoCH^dmg) (4-nitroaniline) is in agreement with the expected formula with tv;o water molecules present. Based on the measured density and crystallographic data the molecular weight of [Co (H2dmg2) (4-methylaniline) ] c£ should be 596. This is greater than its formula weight of 538.9 and the presence of molecules of solvation is expected. Three water molecules or one molecule of the ethanol solvent per formula could account for the difference. Neither of these possi-

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2 Of U (0 o 13 c O U rH (0 o in

PAGE 22

bilities is confirmed by the CHN analysis (see Table 1) . IR spectra of samples as mineral oil mulls between polished plates of fused sodium chloride were recorded on a Beckraan Model IRIO grating spectrophotometer from 4000 to 500 cm" . The spectra were calibrated using the 1601.0 cm absorption of a polystyrene film. IR spectra of selected compounds are reported in Table 2. The IR spectra of the bis (diglyoxime) cobalt (III) complexes with aniline derivatives exhibit many features of similar cobalt complexes with nit, 18 riles and isonitriles described by Batyr et al . The 18 spectra of the cobaloximes shov; the absorption assigned to the C=N stretch between 15 50 cm" and 158 cm . The ab18 -1 sorptions associated with the N-0 band at ca. 124 5 cm and ca. 1095 cm" are present also. A weak absorption in the 1700-1800 cm" range appears in some of the spectra but with lov/ resolution. Peaks in this region have been assigned to the 0---H-0 bridge between the dioximate ligands. The presence of a symmetrical bridge has been 20 suggested to rationalize this low frequency. Absorption spectra in the ultraviolet region were recorded on a Gary Model 15 spectrophotometer. Spectra of solutions were measured from 26.7 kK (375 my) to 47.6 kK (210 my) using the double beam method with the pure solvent as the reference. Solutions of the cobaloxime complexes in methanol (spectroquality ; Matheson, Coleman and Bell) and solutions of the diiphpy compounds in 0.1 M hydrochloric

PAGE 23

10 CM 0) EH (0 3 O t u Q) -P O 0) iH
PAGE 24

11 C •H P c o o CM 0) rH (0 CM E -c O (C U rH «s> U u — CM

PAGE 25

12 0) 0) 0) OJ Eh o I E G, • j:: CM TJ O rM52 I o u CM,— . ^ >i "^^ a, u x: fN ou •H x: Z T3 e^

PAGE 26

13 0) c •H +) O •0 X 0) C4 0) Id o CM I K a • 'O O I O U CNr-. K -''^ a u 4:: cNa •H x; u

PAGE 27

14 acid were used. The UV spectra are reported in Table 3. The UV spectra of all these compounds are dominated by 21 intense charge transfer bands. Yamano et al . report thrde bands in this region for compounds of the formula [Co(H2dmg2)A ] where A is an aniline derivative. These three bands are present in [Co (Hdmg) 2 (clan) 2] C-t and [Co (H2dmg2) (4-methylaniline)2]C£. The band between 25.0 and 27.5 kK (400 to 360 my) was assigned^-*to the charge transfer from the aniline ligand to the cobalt ion. In agreem.ent with this assignment the band for the complex of the more basic 4-methylanJ line at 27.6 kK is lower in frequency than that for the analogous complex of clan at 28.9 kK. The band near 33.0 kK (300 my) was assigned^ "" to the charge transfer from the cobalt ion to the dioximate ligand. The band near 40.0 kK (250 my) was assigned'*'"'" to the intra-Hdmg tt-^-it* transition. The UV spectra of cobaloxime complexes with a cliloride ligand tran s to a substituted aniline shov/ three bands, also. One band is between 27.0 and 33.0 kK (370 to 300 my). The other bands lie near 39.0 kK (255 my) and 43.0 kK (230 my). No assignments have been made for these three bands. The charge transfer spectrum of a solution of [Ni2Ct(H-0) . (dhphpy)]C£-. •2H in 0.1 M HCl exhibits the same absorptions as that of a solution of H2dhphpy (N02)2 ^^ 0-^ ^ HCl. The intense bands at 25.4, 32.7, and 37.3 kK (395, 305, and 268 my) are presumably due to the aromatic system of the ligand.

PAGE 28

15 o

PAGE 29

16 The magnetic moment per nickel atom of (Ni„C-£ (H^O) {dhphpy)]Cf was determined to bo 2.74 D.M. at 40''C. Data 22 23 for this calculation ' were obtained using a Varian A-60A Analytical NMR Spectrometer and aqueous solutions containing 2% by volume t-butanol as the indicator. This magnetic moment is in agreement with those of binuclear complexes of 24 nickel reported by Ball and Blake. Their complexes of the general formula [Ni (dhph) ] _X . 'nll^O (X = Cl, Br, or I) had room temperature effective magnetic moments ranging from 2.79 to 2.89 B.M. As in the case of [Ni (dhph) ] 2X . •nH20, 2+ where two Ni ions are bridged by a conjugated system, spin-spin interaction is indicated in [Ni„C^ (H^O) (dhphpy) ] -

PAGE 30

CHAPTER 3 X-RAY DIFFRACTION EXPERIMENTAL Except where noted in the text, the experimental methods described in this section were used in preliminary crystallographic examination, collection and processing of data, and refinement of trial structures. Data obtained using precession and Weissenberg X-ray 25-27 photographic techniques were used m determining the preliminary space groups and cell constants. After centering fifteen intense reflections d.a computer-controlled Syntex pT dif fractometer and selecting an indexing consistent with preliminary photographs, accurate call constants with estimated standaxd deviations vere obtained from least-squares fittings of 2G, J?,x / and f or those reflections. In each case the orientation matrix for data collection and the unit cell volume with its standard deviation were derived from these data. The calculated density was in agreement with 28 the density measured by the flotation method except in the cases of the metal-containing heterocycles. The specific gravity of the flotation liquid was measured to ±0.01 with a precision hydrometer. Relevant crystallographic data for each of the compounds studied are given in Table 4. The suitability of a crystal for data collection was determined by its physical shape and size, the ease v;ith 17

PAGE 31

10 O ""S" int, ^ ffi ^ CM •» (N U O C31 • O — U U — . ,-,c^ tP >i a a * 'd X H fN a. o ^ c .-rH u o o CQ — «N u a o cN e m 2; w cj O f^ ^ u -"=!• rH o c 1-1 (1) H C (0 o o .-. m4J -u Cr>0 ~QJ e 2 — e fO --' Cli I ^x; x: -— o aa^ «< cr> <^ 'O 'e K Oi e o -H O T) U -H rH — -a (0 o x: (T3 -P CJ Q, O en •— -y-i >-i >i --p u u u c 0) a, c3 o (C 0) e u o c +» cu in to m -p U t/3 f3 1-1 C 3 O Oi E O u (N (N in o O u U u o O CM c o -c C .-I o O in fN u O in Z 00 (N o ;;^ in CN CN sD M-* -^ •^^ ^-^ o CJ CN CJ CJ O U u o fN O (N u u o CM CM o CN CO CN U o (Nl U o o CN o CN x: in CN Dm o o o CN Si o u CN Cn in in CN O CN CN • O ?-. o CN o u u u u u u o rH

PAGE 32

19 -->o ca o o<: XI o<: (t o < c o e o a ro CTl D a\ CO LD C7> n 00

PAGE 33

20 0) xi 0) X Eh

PAGE 34

21 G 0) Q) EH m o o J3 tn C O •H -P
PAGE 35

22 which the reflections wore centered on the diffractometer , and the values of the refined cell constants with their estimated standard deviations compared to the cell constants obtained by photographic methods. All intensity measurements v;ere made with a fyntex PI diffractometer at ambient temperature. All unique refelctions up to a limiting 26 value were measured using a variable speed 0-20 scan technique. The scan rate was determined from a fast throesecond counting scan of the reflection peak and varied linearly from l°/rainute for counting rates of 150.0 c/scc. or less to 24 "/minute for 1500.0 c/sec. or more. The intensity, 1/ was defined: T / 4. \ r /i. J. T ^ \ {bac):ground counts) , I=(scan rate) total scan counts)— ,r: — -, j j. /— ;] . (background to scan rate) Peaks were scanned from 1'^ below Ka, to 1° above Ka„. Measurements of the background count were made at the limits of each scan. The estiraatod standard deviation, o(I), of each reflection was taken to be: „fT\-r f4.^*.-.-\ ^ J\ , (background counts) i 1/2 a(I) = l (total scan counts) + ,r-'T -"j-z r-— r^ J (background to scan ratio) •^ For molybdenum radiation, the incident beam was monochromatized by a low order reflection of graphite. Any changes in the system were detected by measuring four standard reflections after each 96 intensity measurements. A standardized data set was obtained by scaling the data to the initial value of the sum of the measured intensities of the standard reflections. The scaled in-

PAGE 36

23 tensities of duplicate or equivalent reflections were averaged. Reflections with an intensity greater than Ka(I), where K is given in Table 4, were considered reliable. The unreliable reflections with I
PAGE 37

24 factor calculation allowed a sufficient number of reflection phases, a(hkl)'s, to be assigned. The magnitude of the structure factor, | F^^,^ |, and the phase may be defined by 27 the following equations: A^, , = Ef . cos 2TT(hx. + hy. + Iz.) hkl .J 3 D 3 B , , = If. sin 27r(hx. + hy . + Iz ) where f . is the scattering factor for atom j. Additional atomic positions could then be determined through the use of Fourier syntheses of the form: OO 00 CO (XYZ) =E Z Z l^hkl' ^°^ 2tt[ (hX+kY+lZ)-a^j^^] . V h = k=-<» l^-o) The positional coordinates of atoms in the trial structure were estimated froir. the Fourier generated electron density map using a FORTRAN computer program, BOOTHITl, written in the course of this work. A description and listing of BOOTHITl is contained in Appendix A. Alternate structure factor calculations and Fourier syntheses were repeated until all nonhydrogen atoms were located. In the case of a compound not containing a heavy atom but having a centrosymmetric space group, the direct method of symbolic addition was used. The FORTRAN computer programs, FAKE-MAGIC-LINK-SYMPL, developed by E. B. Fleischer, R. B.

PAGE 38

25 K. Dewar, and A.L, Stone ' were used to generate possible solutions to the phase problem. The programs first converted If , I's to normalized structure factors, E's, through the ' obs ' definitions: fp )2 ^ J^ I ,2 (T sin G)/X ^ absolute^ ^2 'obs' and 2 2^2 absolute . i where the scale factor, K, and the overall temperature factor, T, were generated by a Wilson plot; where e was a symmetry factor applied to reflections in special zones; and where f.'s were the scattering factors for N atoms. The programs then assigned symbols representing the phases to six of the largest E's having the greatest number of interactions, i.e., for E^ aiid E there exists E, . For such reflections ' h n. h-m the probability, p, the.t the phase of E, is the same as N E (E E, ) is given by: m h-m ^ -^ m=0 p = 0.5 + 0.5 tanh (-^-lE^i! ^ ^ E^-n,!) a » 1 . 5 m=^ where N ^ j=l 3 with N being the number of atoms in the unit cell and Z. being the atomic number of the j atom. The programs, when given minimum acceptable probability criteria, iteratively assigned relative signs to the phase symbols. Combinations of these

PAGE 39

26 signed phase symbols were finally used in conjunction with their structure factors to generate E-maps. The positional coordinates of most nonhydrogen atoms were determined from one of these E-maps. Structure factor calculations and Fourier syntheses were used to refine the atomic positions and, as in the heavy atom case, to locate any previously unfound nonhydrogen atoms of the trial structure. The trial structure was refined by least-squares 34 minimization of the function: Residual =2w(l|F^^^| If^^^^ID^ where .ow and ' obs ' ' low' ' obs ' ' 1< ' low' — ' obs' — ' high' ^^^ I^high!/l^obsl ^°^ l^obsl > l^high! F, and F . , are constants given in Table 4. Prior to relow high finement, an overall scale factor was chosen such that the sum of F ^ equaled the sum of F , . Isotropic temperature obs ^ calc factors were used in the first three cycles of refinement and then anisotropic temperature factors of the form: exp[-(3j^^h^ + 622^^ ^ ^^33^^ '^ ^12^^ "^ ^13^^^ "^ B23h£)] were used. The reliability index, R, was defined by: K — ' obs

PAGE 40

27 Calculations were performed on an IBM 370/165 computer with programs written or modified by Dr. Gus J. Palenik, except where previously noted. The refinement of each structure is outlined in Table 5.

PAGE 41

28 x:

PAGE 42

29 en U4 o fo

PAGE 43

CHAPTER 4 AN INVESTIGATION OF LIGAND-INDUCED PROTON SHIFT: THE CRYSTAL AND MOLECULAR STRUCTURES OF TRANS -CHLORO (DIMETHYLGI.YOXIMATO) (DIMETHYLGLYOXIME) (4-CHLOROANILINE) COBALT ( III ) DIHYDRATE, TRANS -CHLOROB IS (DIPHENYLGLYOXIMATO) ( 4-CnLOR07U\:iLINE) COBALT (HI) ETHANOLATE, AND TRA_NS~BIS (DIMETHYLGLYOXIMATO) BIS (4-CHLO.HOANILINE) COBALT (III) CHLORIDE. The stability of bis (dimethylglyoxiine) metal coiriplexes has long been known and their importance in both qualitative 37 3 8 and quantitative analysis has been widely recognized. ' Metal complexes of Hdmg have been used to study tlie trans 39 40 41 effect and the trans influence ' of various ligands in octahedral complexes. Since the structural determination of the B, „ coenzynie the trans -bis (dimethylglyoxime) cobalt com42-44 42 plexes have become of considerable interest. Schrauzer has stated that to be capable of mimickiug P^ ^ ^ complex is required only to have a cobalt ion in tiie presence of a strongbinding planar ligand. Because Co(H„dmgp) complexes successfully mimic the reactions of a cobalt ion in the corrin ring and because they are synthetically expedient, complexes of Co(H»dmgp) have been investigated extensively in solution as 45 models for B, „ . Until very recently there have been few structural data on Co(Hpdmgp) complexes. ' ' Except for the work of 46 Palenik et al . no structural investigation has been made of the interaction between the axial ligand and the equatorial Hdmg ligands. This interaction may be of considerable consequence. 30

PAGE 44

31 Although sulfonamides are potent inhibitors of carbonic anhydrase they do not form strong coordination bonds with transition metal ions. Therefore, an interaction of the aromatic ring of the sulfonamide with the carbonic anhydrase pro53 tein has been proposed to make a large contribution to the observed stability of the carbonic anhydrase-sulf onamide complex. Since a cobalt atom can replace the zinc atom in carbonic anhydrase with only a 50% decrease in activity, complexes of Co(H_dmg2) '^^Y pri.^ve to be useful models for investigating the interaction of sulfonamides with carbonic anhydrase. An apparent ligand-induced proton shift (LIPS) was observed in C-^Co (H2dmg2) (si.ilfa) which should be formulated C-^Co (Kpdmg)
PAGE 45

32 cations, successive Fourier syntheses then revealed the locations of all nonhydrogen atoms in the compound. Three cycles of full-matrix least-squares refinement with individual isotropic thermal parameters and then three cycles of leastsquares refinement using. the block approximation with individual anisotropic thermal parameters reduced R to 0.066. A difference Fourier synthesis then indicated the absence of additional nonhydrogen atoms and revealed the positions of all hydrogen atoms. An outline of the refinement is given in Table 5. The refinement was terminated after the parameter shifts for the nonhydrogen atoms were less than one-tenth of their corresponding estimated standard deviations. The scattering factors for cobalt, chlorine, oxygen, nitrogen, and carbon were from Hanson et al.^^ while those for hydrogen were from StewarL e.L_al.-° A list of the observed and calculated structure factors has been published and is available.'''^ The final positional and thermal parameters are given in Tables 6 and 7. St ructure Solution and Refinement for C^Codl^dpg-;,) (clan) -C^H^OH The nonstandard space group P2j^/n was chosen since the standard P23,/c space group would require a very large value for B. The position of the cobalt atom was estimated from a sharpened Patterson function. The location of atoms and the refinement proceeded as in the case of c£Co {Il2dmg) (dmg) (clan) • 2H2O. Two atoms, 0(S1) and C(Si), of an apparent solvent mole-

PAGE 46

33 Table 6 Final Atomic Parameters of Nonhydrogen Atoms for c£Co(H2dmg)(drag) (clan)^ Atom

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34 Table 6 extended ^33 ^12 ^13 ^23 276(4) 822(17) 219(13) 157(9) 53(1) 78(4) 25(3) 14(2) 138(2) 65(7) 46(7) 46(4) 36(3) 168(14) 7(9) 44(6) 32(3) 167(13) 70(9) 33(6) 41(3) 199(14) 74(10) 70(6) 30(3) 199(14) 31(9) ,25(6) 37(3) 123(14) 29(10) 50(7) 35(3) 108(14) 24(10) 26(7) 35(3) 71(13) 30(9) 19(6) 41(3) 123(14) 41(10) 39(7) 35(3) 99(13) 21(10) 12(7) 53(4) 101(17) 25(13) 41(9) 51(4) 73(16) 30(13) 14(8) 76(5) 190(21) -5(16) 55(10) 62(5) 214(22) 50(16) -6(10) 56(4) 134(18) 47(14) 44(9) 60(5) 110(17) 52(13) 24(9) 102(7) 347(31) 148(24) 106(14) 73(6) 301(28) 37(20) 11(12) 44(4) 72(15) 23(11) 44(8) 47(4) 89(17) 4(13) 28(9) 42(4) 95(19) 4(14) 8(9) 82(6) 61(18) 23(16) 39(10) 69(5) 99(20) 83(16) 95(11) 52(4) 104(18) 56(13) 52(9) 80(4) 241(16) 102(11) 100(8) 53(3) 295(16) 20(10) 22(7)

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35 Table 7 Final Parameters for the(clan)^

PAGE 49

36 cu]c were located before refinement. The scheme of the refinement is outlined in Table 5. Although the compound was crystallized from ethanol, difference I'ourier syntheses at various stages of refinement failed to indicate the position of an additional atom in the solvent molecule. Because a large region of relative high electron density existing near C(fl) could be indicative of an atom with high disorder and because ethanol v/as the solvent, a molecule of ethanol was assumed to be present for the purposes of determining the formula, molecular weight, and density . The cobalt, chlorine, oxygen, nitrogen, and carbon 29 scattering factors wore taken from Hanson e t a 1 . and those for hydrogen from Stewart et al . Table B-1 is a list of observed and calculated structure factors for C£Co (H2dpg2)~ (clan) . The final positional and thermal parameters are shov/n in Tables 8 and 9. Struc ture So l ution and Refinement for "ICo (Hdmg) 2 (clan) 2] C?. With one molecule per unit cell in the centric PI space group the cobalt atom and the chloride anion were required to lie on centers of symmetry. The sharpened Patterson function was ill agreement with tlie chloride ion at 0--iO when the cobalt atom is placed at 000. The remaining atoms were located in a similar manner as in CgCo (H2dmg) (dmg) (clan) . An outline of the refinement is given in Table 5.

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37 Table 8 The Final Atomic Parameters for the Nonhydrogen Atoms of ClCo (H2dpg)2

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38 Table 8 extended B 33 '12 6 13 3 23 19(0) 40(1) 100(3) 21(3) 16(3) 20(3) 21(3) 34(4) 13(3) 26(4) 20(3) 16(3) 23(4) 18(4) 23(4) 28(5) 23(4) 15(4) 17(4) 28(5) 30(5) 36(6) 45(6) 46(6) 37(6) 33(5) 39(5) 29(5) 45(6) 43(6) 32(5) -7(3) 8(5) 71(9) 12(11 -17(16 -35(13 -18(13 -9 (13 23(11 7 (15 15(1^ -12(14 5(16 -5(18 20 (17 11(17 4 (15 24 (15 43(17 26(16 -5(18 17 (19 45(18 58(19 19(23 69(17 5(17 10(21 12(19 28(2?. 7(22 2(1) 11(3) 96(5) 6(6) -8(6) 3(6) -4(5) 7(8) -6(6) -1(8) 6(7) 13(6) 16(9) 7(9) 20(9) -8(10) 12(9) -4(8) 3(3) -] (10) •18(10) -7(11) 4(12) 40(12) 44(12) 9(10) 31(10) 22(11) 9(11) 30(11) 11(11) -4(2) -13(4) -15(7) 26(8) 7(13) 8(9) 12(10) -15(12) 14(8) 7(12) -21(11) 6(11) 20 (13) 0(13) 23(14) 5(13) -2(12) 7(11) -9(12) 30(12) 20(14) 15(15) 2(15) 20(15) 70(17) •29(14) 4(15) 2(16) 46(16) 13 (19) 2(17)

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39 Table 8 continued Atom X y z ^^^ ^22 C(1B) 6675(9) 2815(14) 3687(7) 61(9) 113(16) C(2B) 7444(9) 2801(13) 4142(7) 59(9) 89(15) C(3B) 7498(9) 3363(15) 4781(7) 56(10) 189(23) C(4B) 6828(9) 4051(16) 4937(7) 59(10) 207(22) C(5B) 6047(10) 4094(14) 4476(7) 73(11) 148(19) C(1C) 664(9) 1226(12) 3750(7) 66(10) 73(14) C(2C) 20(9) 872(12) 4199(7) 56(10) 96(16) C(3C) -212(9) 1576(14) 4700(8) 32(8) 183(23) C(4C) 184(9) 2563(12) 4813(7) 61(10) 112(17) C(5C) 826(8) 2872(11) 4368(6) 60(8) 41(11) C(1D) 593(9) 2121(12) 1437(6) 54(8) 83(14) C(2D) -224(9) 1992(14) 1045(7) 56(9) 116(16) C(3D) -951(9) 2410(12) 1345(7) 50(9) 105(17) C(4D) -888(8) 2847(12) 2044(7) 42(8) 77(14) C(5D) -69(8) 2975(12) 2447(6) 30(7) 63(12) 0(S1) 1418(9) 4904(10) 944(5) 190(13) 136(13) C(S1) 1450(26) 4854(22) 182(12) 512(49) 196(30) a 4 . . All values are x 10 . The estimated standard deviations are given in parentheses. The temperature factors are of the form: exp[-(B^^h2 + 622^^^ "^ ^33^^ "^ ^12^^^ "^ ^13^^^ "^ 3^ok-c) J .

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40

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41 Table 9 Final Parameters for Hydrogen Atoms for C£Co (Il^dpg„ ) (clan) Atom [Bonded to] Distance x y z B H(B1)

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42 The scattering factors for cobalt, oxygon, nitrogen, and 29 carbon were from Hanson et al . , those for hydrogen wore from Stewart et al . , and those for chlorine were from Doyle and Turner. The observed and calculated structure factors are given in Table B-2. Lists of final positional and thermal parameters may be found in Tables 10 and 11. Results and Discussion The atomic numbering and thermal ellipsoids of C£Co{H2dmg) (dmg) (clan) , c£Co (H2dpg2) (clan) , and [Co (Hdmg) 2 (clan) 2]54 CI are shown in ORTEP drawings in Figures 1, 2, and 3, respectively. The individual bond distances for these three compounds together with those of tv;o related compounds, C€Co(Il2dmg) (dmg) (sulfa) and [Co (Hdmg) 2 (an) 2] C^, ^^ are tabulated in Table 12. The corresponding bond angles are given in Table 13. In each case the tv;o dmg or dpg groups are approximately planar as demonstrated by the deviations from least-squares planes in Tables 14-16. The dmg groups of each complex are linked by two intramolecular hydrogen bonds (see Table 17) . As in the case of C^Co (H2dmg) (dmg) (sulfa) ''^ the hydrogen bridges between the dmg groups in C^Co (H2dmg) (dmg) (clan) were found to be asymmetrical with both hydrogen atoms bonded to the same dmg ligand. The 0(21)-H(B2) and 0(22)-H(Bl) diso tances of 1.13(8) and 1.16(8) A, respectively, compared to the 0(12) • • •H(B2) and (11 ) • • -H (Bl) distances of 1.36(8) and o 1.37(8) A indicate the formulation H2dmg and dmg for the two

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43 Table 10 " The Final Atomic Parameters for Nonhydrogen Atoms of [Co(Hdmg)2 (clan)2lC£.^ Atom

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44 Table 10 extended ^33 ^12 ^13 ^23 332(3) 226(12) 169(9) -43(6) 873(8) 451(29) 1194(26) 13] (15) 482(7) -1987(79) -431(28) -982(29) 57(1) 9(5) 11(4) -12(3) 57(1) 40(6) -20(4) 15(3) 45(1) 28(6) 30(4) -9(3) 47(1) 26(6) 30(4) -21(3) 41(1) 53(6) 7(4) -7(3) 47(2) 47(8) 27(5) -24(4) 63(2) -25(9) 59(6) -42(5) 72(2) -85(12) -3(8) -93(6) 49(2) 2(15) -11(3) -59(7) 51(2) -22(15) 64(8) ] (7) 52(2) -11(10) 36(6) -12(5) 52(2) 42(7) 73(6) -4(4) 46(2) 68(8) 5o(6) 6(4) 77(2) 12(9) 109(7) 16(5) 68(2) 68(11) 47(8) 75(6)

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45 Table 1j . Final Parameters for Hydrogen Atoms for [Co (Hdmg) 2 (clan)^^^' Atom [Bonded to] Distance x y z B H(B1)[0(12)] 1.07(3) -408(8) -35(4) -133(3) 5.5(0.8) H(2)[C(2)] 0.85(3) 280(4) 321(3) 190(2) 3.5(0.6) H(3)[C(3)] 0.91(4) 447(6) 361(4) 3C6(3) 6.0(0.8) H(5)[C(5)] 0.98(4) -92(6) 105(4) 431(3) 6.6(0.9) H(6)[C(6)] 0.96(3) -248(5) 73(3) 244(.?) 3.9(0.6) H(7)[N(1)] 0.88(2) -299(4) 146(3) 64(2) 2.1(0.5) H(8)[N(1)] 0.94(2) -52(4) 262(3) 49(2) 2.7(0.5) H(11)[C(13)] 0.90(4) 349(6) 440(4) -131(3) 5.7(0.8) H(12)[C(13)] 0.89(4) 417(7) 315(5; -185(4) 9.0(1.2) H(13)[C(13)] 0.91(4) 513(6) 353(5) -67(3) 7.3(1.0) H(14)[C(14)] 0.86(4) -181(7) 217(5) -314(3) 9.0(1.2) H(15)[C(14)] 0.80(5) -14(8) 300(6) -274(4) 10.0(1.3) H(16)[C(14)] 1.01(5) -213(8) 337(6) -252(4) 11.0(1.4) • ^The hydrogen atom is given follov7ed by the atom to which it is bonded in brackets, the corresponding bond distance (A) , the positional parameters with estimated standard deviations (x lO"*"-^) , and the isotropic thermal parameters (a2) .

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u n o •H -P 0) o c Q) Q) U XI •H E 0) O > n3 .c; CU Ifi £ (N (tj K S H CN • 'C Q) ^ C M C nJ ^ nj Cn>H W H o e -^ o ^ -p — O f: U TJ Ti i O Eh U H-4 • o w c o •H W (0 --H U <-i E-« >i P i5 p o

PAGE 60

47

PAGE 61

(0 0) -P b-P C -I o c •H V^ Ct u o •H > E «« o x: +j (d Q) O x: o -p o tP o •H o o Xi in tn W \xi U CM O lO'd 0) w d 3 o Cri • CO P4 r-' O rH m V — Ci ^ 0) tT" O D. W fa ^o CM >i O Ci u .a u O CO Tl tn-iH f-; o ? fi. CU P5 H E-i (fl f^ E O V^ O < -P

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49

PAGE 63

g 0) Xi +» •o c Id c H d)

PAGE 64

51

PAGE 65

52 Tabic 12 Selected Interatomic Distances (X) in Some Cobaloxime Complexes with Their Estimated Standard Deviations.^ C£Co(H2dmcj) (clan) C-CCo (Il2dpg) 2 (clan) Co-N{l)

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53 Table 12 extended C£Co(H2dmg2)(sulfa) '^ [Co (n2ding2)(clan) 2] C£ [Co (H2dmg2)(an) 2] C£ 2.023(8) 2.003(2) 2.001(5) 1.870(8) 1.906(2) 1.885(6) 1.884(8) 1.889(2) 1.889(5) 1.323(11) 1.340(3) 1.353(6) 1.344(11) 1.362(3) 1.333(6) 1.289(14) 1.299(3) 1.286(10) 1.293(13) 1.290(3) 1.303(10) 1.494(16) 1.477(4) 1.463(7) 1.532(17) 1.483(4) 1.482(12) 1.488(16) 1.485(4) 1.476(11) 2.507(11) 2.495(3)* . 2.491(8)* 1.50 1.44(3) 1.29 1.60 1.07(3) 1.21 2.235(3) 1.905(8) 1.896(8) 1.326(10) 1.338(11) 1.292(12) 1.290(14) 1.447(17) 1.494(17) 1.488(16) 2.479(11) 0.90 1.04

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54 Table 13 SG^o.oted Intramolecular Angles (°) in Some Cobaloximo Complexes with Their Estimated Standard Deviations.^ C^Co(H dmg2) (clan) C£Co(h2dpg2) (clan) N(l)--Co-N(ll) 90.5(2) 94.8(4) N(l)-Co-N(12) 91.5(2) 92.1(4) N(l)-Co-N(21) 88.4(2) 87.1(4) N(l)-Co--N(22) 88.6(2) 88.6(4) N(ll)-Co N(12) 82.6(2) 81.3(4) N(ll)--Co-N(22) . 98.8(2) 100.0(4) N(ll)-Co-N(21) 178.8(2) 177.5(4) N(12)-Co-N(21) 98.1(2) 97.0(4) N(12)-Co-N(22) 178.6(2) 178.5(4) N(21)-Co-N(22) 80.6(2) 81.7(4) C£(l)-Co-N(ll) 90.6(2) 87.7(3) C^(l)-Co-N(12) 90.6(2) 89.1(3) C£(l)-Co-N(21) 90.5(2) 90.4(3) C£(l)-Co-N(22) 89.4(2) 90.2(3) cr.(l)~Co-N(l) 177.8(2) 177.4(3) Co-N(l)-C(l) 119.7(4) 118.6(8) Co-N(ll)-O(ll) 121.9(4) 123.3(7) Co-N(12)-O(12) 122.2(4) 121.2(8) Co-N(21)-O(21) 123.2(4) 123.5(8) C;o-N(22)"0(22) 123.3(4) 120.7(7) Co-N(ll)-C(ll) 116.0(4) 116.7(8) Co-N(12)-C(12) 115.6(4) 114.1(9) Co-N(21)-C(21) 116.6(4) 116.8(8) Co-N(22)-C(22) 117.0(4) 117.4(8) 0(11)-:](11)-C(11) 122.1(5) 119.7(9) 0(12)-N(12)-C(12) 122.3(5) 123.8(11) 0(21)-N(21)-C(21) 120.3(5) 119.4(10) 0(22)-N(22)-C(22) 119.8(5) 121.7(10) N(ll)-0(11) -0(22) 99.7(3) 95.9(6) N(12)-0(12)-0(21) 99.7(3) 99.2(7) N(21)-0(21) -0(12) 96.9(3) 98.2(7) N(22)-G(22) -0(11) 96.0(3) 100.1(6)

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55 Table 13 extended 46 52 C£Co(H dmg2)(sulfa) [Co (H2dmg2)(clan) 2] C^ [Co (H2dmg2)(an) 2] C£ 90.5(3) 89.8(1) 91.5(4) 91.7(3) 93.2(1) 93.0(5) 89.3(3) 87.8 (3) 82.0(4) 80.8(1) 80.8(3) 98.7(4) 179.3(4) 98.7(3) 179.2(4) 80.6 (3) 89.6(3) 88.5(3) 90.5(3) 91.9(3) 179.7(2) 119.1(6) 119.7(1) 119.5(7) 123.0(6) 121.3(1) 121.4(6) 122.6(6) 122.7(1) 122.9(7) 121.6(6) 123.6(6) 116.4(7) 116.9(2) 116.0(9) 117.4(7) 117.7(2) 117.8(9) 116.3(7) 116.8(7) 120.5(9) 121.8(2) 121.8(12) 120.0(8) 119.6(2) 119.2(10) 122.2(8) 120.1(9) 98.3(6) 97.8(6) 99.2(5) 96.8(6)

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56 Table 13 continued C£Co(H dmg ) (clan) C£Co(H2clpg2) (clan) N(ll) N(ll) N(12) N(12) N(21) N(21) N(22) N(22) C(13) C(14) C(23) C{24) -C ( 1 1 -C(ll -C(12 -C(12 -C(21 -C(21 -C(22 -C(22 -C(ll -C(12 -C(21 -C(22 -C(12) -C(13) -C(ll) -C(14) -C(22) -C(23) -C(21) -C(24) -C(12) -C(ll) -C(22) -C(21) 112.8 (6) 122.9(6) 113.1 (6) 122.5(6) 113.5(6) 112.4 (7) 112.3 (6) 123.2(6) 124.2(6) 124.4 (6) 124.1(6) 124.4 (6) 112.1(10) 125.6(11) 115.5(11) 119.5(11) 112.2(10) 120.9(11) 111.9(10) 126.0(11) 122.3 (11) 125.0(11) 126.8(11) 122.2 (10) The atomic numbering of Co (H2dmg2) (an) 2c/* has been changed to correspoiid to that of compounds of this work.

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57 Table 13 continued extended C£Co(H2dmg2)(sulfa)'^^ [Co (H2dmg2)(clan) ^]Cl [Co (H2ding2)(an) ^]C.^^ 113.3(9) 112.2(2) 112.4(10) 125.0(10) 125.0(2) 124.6(16) 110.7(9) 112.5(2) 112.2(9) 124.0(10) 124.1(2) 125.0(16) 113.1(9) 120.7 (10) 113.1(9) 122.9(10) 121.7(10) 122.9(2) 123.0(12) 125.3(10) 123.4(2) 122.9(13) 12 6.1(10) 123.6(10)

PAGE 71

58 ligands. This is in contrast to results reported for various Co(H2dmg2) complexes^^ ''*''' ''^' ^° ' '^^ as well as for Fo(H2dmg2)-(imidazole) 2/^^ Ni (H2dm92) , '"'^ and Cu(H2dmg2), where either the hydrogen bridges were assumed to be equidistant from the tv70 oxygen atoms or the ligands were monoprotonated. The assumption of a symmetrical bridge may have in part been based on the earlier TR spectroscopic work on M(H2dmg2) complexes where the v^eak band due to nn O-II vibration near 1725 cm was assumed to indicate a very sl)ort aiid symmetrical O-H-O bridge. "^^'^^ McFadden and McPhail"'"'' reported the structure of Co(H2dmg2) (CH3) (H2O) ii' which both bridging hydrogen atoms if ordered are required crystallographi cally to be on one dmg ligand. No comment" was made concerning the bridging hydrogen atoms. Although both hydrogen bridges in C^Co {H2dpg2) (clan) appear to be shifted toward one dmg v.'here the 0(21)-H(B2) and o 0(22)-H(Bl) distances are 1.16(10) and 1.17(15) Awhile the 0(12)--H(B2) and 0(11)-H(l!l) distances are 1.30(10) and 1.41 o (14) A, the experimental uncertainty is too large to show that result to be significant. The hydrogen bridges in [Co (Hdmg) 2 (clan) 2] c£ are not symmetrical and each dmg is singly protonated. The 0(12)-H(B1) distance is 1.07(3) A and the (11) • • -H (bl) distance is 1.44 o (3) A. The gross structure is very similar to that of tCo(Hdmg)2(an) 2lC-^Bowman et al . suggested the N-0 distance to be a sensitive indicator of the position of the bridging hydrogen.

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59 Table 14 Deviations and Equations of Selected Least-Squares Planes in C£Co(H2dmg) (dmg) (clan)^ ° +3 (a) Deviations (A x 10 )

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Table 14 continued ^The deviations of atoms used to define the plane are marked with an asterisk. GO Plane

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61 Table. 15 Deviations and Equations of Selected Least-Squares Planes a in C^.Co(H2dpg ) (clan) ° +3 (a) Deviations (A x 10 )

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62 Table 15 continued Plane 1 Plane 2 Plane 3 Plane 4 C(1B) 1094 C(2B) 1237 C(3B) 427 C(4B) -641 C(5B) -821 C{1C) 1232 C(2C) 1380 C(3C) 3C1 C(4C) -734 C(5C) -827 C(1D) 571 C(2D) 554 C(3D) -230 C(4D) -874 C(5D) -8^38 r p (b) Coefficients of the Plane Equation"^" A>: + BY ICz " D Plane

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63 Table 16 Deviations and Equations of Solected Least Squares Planes in po ( Hdmg ) ( c 1 an )2 ]Cl^ (a) Deviations (A x lO'*'"^ ) Co 0(11) 0(12) N(ll) N(12) C(ll) C(12) C(13) C(14) N(l) C(l) C(2) C(3) C(4) C(5) C(6) Cl{2) Plane 1

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64 X I Q VO VO >X> 00 CO ro CM (N o n VD

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65 Dissimilar N-0 bond lengths should indicate the hydrogen is not symmetrically located and is closer to the dmg with the longer bond. This holds true in C£Co(H2drag) (dmg) (clan) where the N-0 distances appear to be different. The N (21) -0(21) o and N(22)-0(22) distances of 1.348(6) and 1.359(6) A in the diprotonated dmg are longer than the N (12) -0(12) and N(ll)o 0(11) distances of 1.329(6) and 1.337(6) A in the dianionic dmg. Using the significance test described by Cruickshank and Robertson the N (21) -0(21) distance is possibly longer than the N (12) -0(12) with a t^ value of 2.2 4 and the N(22)0(22) bond is significantly longer than the N (11) -0(11) bond with a t value of 2.59. Also, in [Co (Hdmg) 2 (clan) 2] C£ the o N(12)-0(12) bond of 1.362(3) A is significantly longer than o the N (11) -0(11) bond of 1.340(3) A, v/here the bridging hydrogen atom is bonded to 0(12). Neither the N-0 distances nor the bridging O-H distances in c£Co (H2dpg2) (clan) are significantly different. In [Co (Hdmg) 2 (an) 2] CZ where the hydrogen atoms are not significantly removed from a symmetrical position, the N (12) -0(12) distance is shorter than that of N(ll)0(11). The difference in these two bond lengths of 1.333(6) and 1.353(6) A is of possible significance (t^ = 2.36). The sensitivity of the N-0 bond as an indicator of the bridge position is questionable. The N-0 bonds are not significantly different in C'CCo(H2dmg) (dmg) (sulfa) when both bridging hydrogen atoms are shifted to one dmg. In the closely related dimethyl ( 3, 3 '-trimethylenedinitrilo) bis(butan-2--oneoximato) cobalt (III) complex the two N-0 distances are e::ual

PAGE 79

6C even though an asyinmetric hydrogen bridge is clearly indicated by the difference Fourier syntheses. Although a difference in the N-0 bond lengths as a function of protonation is reasonable, there are very few structures so precisely determined that this comparison can be made. Hence, no general conclusion may be made. Hov;evcr, when a significant difference in the N-0 distances has been found and the bridging hydrogen atom has been precisely located, the hydrogen atom is associated with the longer N-0 bond. Another point in support of the formulation C£Co(H2dmg)(dmg) (clan) is the difference in the Co-N bond lengths. The o Co-N distances on the ll2dmg side are 1.908(5) and 1.906(5) A o compared to distances of 1.872(5) and 1.884(5) A on the dmg side. The differences in the Co-N bond lengths are significant and the shorter distances involve the dianionic group. This holds true in the other cases where the presence of both H2dmg and dmg ligands has been indicated. In CcCo (H2diTig) (dmg) (sulfa) ' and in Co (H2dmg2) (CII^) (H2O) ^'" the distance.s from the cobalt atom to the dianionic ligand are shorter than the distances to the neutral H2dmg ligand. This is not the case in C£Co (ri2dpg2) (clan) where the distances from the cobalt atom to what would be the dpg didnionic ligand, 1.9 35(11) and 1.908 o (9) A, appear to be longer than the corresponding distances to the n2dpg ligand, 1.887(10) and 1.897(9) A. These differences together with the apparent positions of the bridging hydrogen atoms ( vide supra ) in C£Co(H2dpg2) (clan) are of questionable significance.

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67 For the mononegative ligands in [Co (Hdmg) „ (clan) 2] C^ the Co-N distances are significantly different. However, N(12) which is l:ionded to the protonated oxygen atom is closer to the cobalt atom than is K(ll) with distances of 1.889(2) and 1.906 o (2) A, respectively. The same relationship holds in Fe(?Idmg)255 (imidazole) 2 r the only other M(Hdmg)2 complex whose X-ray structure precisely places one bridging hydrogen on each dmg and shov/s a significant difference in the metal to nitrogen distance. /in unsyixmietrical hydrogen-bonding system involving two similar atoms may be fluxional. In such a system two equilibrium positions, i.e. potential v/ells, exist for the hydrogen atom. Each of these positions may be considered as having tiie hydrogen atom covalently bonded to one atom and hydrogen bonded to the other. For the system to be truly fluxional the energy barrier betv/een the tv/o positions must be thei:aally accessible. Depending on the relative depths of the potential wellr. , tlie energy barrier betv^een them, and the thermal energy of the system the position of the hydrogen atom as indicated by X-ray diffraction experiments would vary. Because of the diffuse appearance of the bridging hydrogen atoms of the M(n2dmg2) complexes in difference Fourier syntheses, a fluxional system with two potential wells of unequal depth seems reasonable. The relative populations of the two positions will depend soniev7hat on the depths of the potential wells. The experimentally determined position (or positions) of the hydrogen atom v/ill reflect these populations. As the depths of the

PAGE 81

68 potential wells approach equivalence and as the energy barrier between them becomes smaller the position of the hydrogen atom will become experimentally more uncertain. A fluxional system could, in part, account for tlie difficulty iii precisely locating the bridging hydrogen atoms in M(H2dmg2) complexes. The orientation of the 4-chloroaniline ligand in the complexes of this study is quite intriguing. A projected view down the Co-N(l) bond for C£Co{H2dmg) (dmg) (clan) is shovm in Figure 4. A similar view for [Co (Hdmg ) 2 (clan) 2] C£ is given in Figure 5(a) and one for C^Co(H2dpg2) (clan) is given in Figure 5(b) . In CeCo(H2dmg) (dmg) (clan) , as in C£Co(H2dnig) (dmg) (5:.ulfa)^^ the aromatic ring of the aniline is oriented over the dianionic dmg ligand. The orientation angle, i.e. the dihedral angle between the planes having Co-N(l) in common with one containing C(l) and the other containing the bisector of the angle N (11) -Co-N (12) , for C£Co (K2dmg) (dmg) (clan) is 0.9° and for C£Co(n2dmg) (dmg) (sulfa) is 1.8° us given in Table 18. In [Co(Hdmg) 2(clan) 2]C£ and in [Co (Hdmg) 2 (an) 2]C£ the ben7ene rings are skewed relative to the equatorial ligands with orientation angles of 53.9° and 58.3°, respectively. It seems significant that in the former pair of Co (H^dmg) (dmg) type complexes the rings align while in the latter pair of Co (Hdmg) 2 type complexes the rings are skewed. Although tho benzene ring of the aniline is tipped from being parallel to the dmg plane by ca. 30° as in other similar complexes (see Table 18) the alignment and the distances between the two planes in C£Co(H2dmg) (dmg) (clan) suggest a ir-type interaction. The

PAGE 82

o -I C) CN u Ui CP o -H u CJ M O I o o o l-l n) 0) •H > (U +) o 0) •n O M &.

PAGE 83

70 O oCQ .X O

PAGE 84

o CM o o o XI c nJ =^ CJ o (M 6 in w QJ O O :3 I o o O H I > d (U -p o 0) -n O U

PAGE 85

72

PAGE 86

73 en o fH c E o u o CM a, K O O u rH o CM o 10

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74 0) c o y, I 00 I-l Q) iH a EH o-i ^-^ Cf^ • • o • (N 1X> CO >X) rO OO rH CO n 00 in o r>— , r• • o • CO CTi CO

PAGE 88

75 distances from the dmg plane to C(l), C(2), and C{6) given o in Table 14 are substantially less then the 3.40 A interplanar distance in graphite. A proton transfer occurring from one Hdmg ligand to the other would increase the electron density within the ir-system of the formed dianion. An interaction by v/hich the filled it orbitals of the dmg overlap v;ith the empty ii* orbitals of the aniline v;ould enhance the basicity of the aniline ligand. The complex formed v;ould be stronger than might be expected based on the K, value alone. This same argument applies to C-£Co(H-dmg) (dmg) (sulfa) which was the first example of ligand-induced proton shift in a molecular complex. While the positions of the bridging protons in C-^Co (H^dmg) (dmg) (clan) and [Co (Hdmg) 2 (clan) 2] C^ are well defined, the bridge in C.£,Co (Hpdpg-^) (clan) is ill defined and the orientation angle of 36.7° is an intermediate value (see Table 18). The 0---0 distances in this complex shov; more variation than those in other related complexes as sho\;n in o Table 12. The 0.08 A difference in the 0...0 distances is the same as for the corresponding N-'-N distances. The N(12)''' N(21) separation is 2.836(15) A and the N (11) • • 'N (22) diso tance is 2.914(13) A. Concurring with these observed distances, the N(12)-Co-N(21) angle of 9 7.0(4)° is more acute than the N(ll)-Co-N(22) angle of 100.0(4)°. None of tlie other compounds examined shows any significant differences in the corresponding distances and angles between the diglyoxime ligands .

PAGE 89

76 A comparison of mean bondiny distances for each of the reported Co(H2dmg2) complexes may be made from Table 19. There appears to be little variation in the average Co-N distances or in the average dimensions within the equatorial dimethylglyoximc ligands as a function of the axial ligand.^ Those complexes having chloride as an axial ligand show a definite variation with the nature of the trans ligand. The longest Co-Ct distance is found where tpp is the trans ligand. This is not surprising since phosphines are knovm to have a very large tr ansinfluence but the small influence the tpp ] igand exerts on the tran s -chlorine atom compared to 40 that of an ammonia ligand is unexpected. There is no significant difference in the Co-N(l) distance involving a clan ligand v;hether it is t rans to a chlorine atom or trans to another clan ligand. The trans -influence appears to occur in Co (K2dii-ig2) complexes but not to a large extent. The Co-Y distances in the XCo(H2dmg2)Y complexes where Y is a ligand with an sp nitrogen, increase in the following order of Y: NH^ < an '>clan < sulfa (see Table 19). This series can be rationalized in terms of the relative K, 's for sulfa (2.3 X lO"-*-^),^^ clan (9.6 x lO""'--'-),^^ aniline (4.0 x 10~ ),^^ and ammonia (1.3 x 10~ ) . Bruckner and Randaccio did not consider the J'j-'s of the different nitrogen donors in their argument of the trend in trans influencing ligands, X, upon the Co-N bond. The same Co-N distances were used for NH^ and aniline complexes in their argument for basing the extent of trans in fluerrce on the a-donor power of the t rains

PAGE 90

77 U) i-H u C^ o n O I CO . u i CO I o u I o u IT) CN n o ^-vo u~> (N CO 0-) en

PAGE 91

78 0) '0 c a) -p y. 0\ r-i (1) rH a Eh (1) U C
PAGE 92

79 ligand as are presented here. In comparing C-^Co (H2dpg2) (clan) with C-CCo (H2dmg) (dmg) (clan) the distances from the cobalt atom to the equatorial nitrogens in the H2dpg complex are longer and the distances to the axial ligands are shorter in the same complex. Because the phenyl substituents are inductively more electron withdrawing than methyl groups , Hdpg should be a v/eaker Lev;is base than iJdmg. The equatorial distances to the Hdpg should, therefore, bo longer. From an electronic standpoint the cobalt ion in the Hdpg complex would be more positively charged and a better Lev;is acid toward the axial ligands than in the Hdn^g complex. From a steric point of view the axial ligands are afforded a wider path of approach and v/ill, therefore, be closer to the central cobalt ion. v/hen the equatorial ligands are farther away . The benzene rings in the clan ligands of Ci^.Co (IlTdmg^J " (clan), C£Co (H2dpg2) (clan) , and [Co (Hdmg) 2 (clan) 2]CC are planar (see Tables 14-16) having average C-C values of 1.376(3), o 1.380(10), and 1.378(3) A, respectively, with individual values reported in Table 20. The phenyl rings of the Hdpg ligands of C^Co (H2dpg2) (clan) are also planar with pertinent values and equations of least-squares planes given in Table 21 The crystals of C-£Co (H2dmg) (dmg) (clan) are held together by six hydrogen bonds where there are eight hydrogen atom.s capable of hydrogen bonding. Relevant hydrogen-bonding data are presented in Table 17. Although the 0-H---0 bridges between the H2d;ag and dmg groups are not synv.aetrical, th.-; O-II

PAGE 93

80 o -p E H 4J U V( •H 0) x: ? m (1) H o ns r--| 0) ;Q -!-> fct C •H •ci X o o u o (0 0) < c o « •si u CM c" rH u CM K O U r ! u a, CM o <^ u U e K O u u in Id ;^ c; o (0 to (U o C (1) «0 Q +t W Ti •H H -d ci C To o -n « to in o< V c P tn •H Q "-f IT, Vi) »tf' ':? rO ro CO ro tr>-) 00 in o ro r-! r^ iH r-i rH O CN O rH (N CM o a\ £X> O (O •<-' -^ rH r-l -I rH •1 CN m o rm CN] .H rH (vj n' <.o e5 ^1 vo •>-j< ro CM ro 00 ro 'a* rCO CD o r-l o o rH r-l O -^ '-^ r-( CTN CX) OT OO o CO (» cyi '^r rCO r~ rro 00 oo ro oo ri rH -1 I '--1 t m '3' in ^^ ,-. ^~. c^ r-i I: <3< in "vO ^-^ ?», C) a O CJ U CN

PAGE 94

81 Table 21 Bond Distances, Bond Angles, and Least-Squares Planes of the Phenyl Rings in C£Co (H2dpg2) (clan) with The.ir Estimated Standard Deviations. 23 24 (a) Distances C{n)-C{lt) C(n)-C{5.e) C{ll)-C{2l) C{2l)-C{3l) C(3£)-C(4.£) C(4^)-C(5^) . (b) Angles (") C(n-2)-C(n)-C(U) C(n-2)-C(n)-C(5£) C(n)-C(U)-C(2£) C{ll)~C{2l)-C{3l) C{2Z)-C{3l)-C(Al) C(3£)-C(4l)-C(5£) C(4£)-C(5£)-C(n) C(5£)-C(n)-C(U) o (c) Deviations (A Rings C(n) C(U) C{2l) C(3l) C{4l) C(5^) C(n-2) n = 13 £ = A 14 B D 1.3G3(18) 1.411(20 1.421(20) 1.396(20 1.368(19) 1.371(20 1.370(21) 1.367(20 1.352(20) 1.391(23 1.37.1(20) 1.390(20 123.9(11) 119.3(12 119.9(11) 120.9(12 122.8(13) 120.6(13 119.5(13) 119.3(14 120.5(13) 121.0(14 120.0(14) 120.4(14 121.0(13) 118.4(14 116.2(12) 119.8(13 X 1.370(19) 1.426(17) 1.356(17) 1.458(18) 1.432(19) 1.385(19) 1.351(21) 1.401(20) 1.371(23) 1.397(20) 1.409(18) 1.397(18) 120.9(11) 121.7(11) 121.2(11) 120.6(11) 122.3(12) 122.6(12) 117.0(13) 117.7(13) 122.2(14) 122.5(13) 118.7(13) 120.2(13) 121.7(12) 119.0(12) 117.9(12) 117.7(11) + 3 10 ) from Least-Squares Planes of Phenyl 2 -7 10 -10 5 -2 -3 41 -14 -31 48 -20 -24 172 -3 8 15 -29 3 19 -16 3 -12 24 -28 20 -7 20 (d) Coefficients of the Plane Equation PX + QY + RZ = S P Q R S Phenyl A Phenyl B Phenyl C Phenyl D -0.5815 -0.4144 -0.6482 -0.1592 0.5296 -0.7511 0.3950 -0.8986 -0.6176 0.4990 -0.6509 0.4088 4.7459 3.1793 4.0341 1 . 3 6 ^: 2

PAGE 95

82 distances arc longer than might be expected. The tv;o hydrogen atoms on N(l) of the clan ligand both hydrogen bond to different water molecules. The hydrogen atoms of one water molecule, 0(w2), form reasonably strong hydrogen bonds to 0(12) and C£(l) . The hydrogen atoms on 0(wl), however, have only short contacts with angles indicating only v;eak hydrogen bonds. V^hile [Codldmg) 2(clan) 2]C£ and C£Co (H2c3pg2) (clan) both exhibit the hydrogen bonding botv.'een the equatorial ligands, Ci^Co(n2dpg2) (clan) has no interraolecular hydrogen bonds. While the hydrogen atom on the solvent molecule was not located, a hydrogen bond may exist between 0(S1) and 0(22). Each molecule of [Co(ndmg) 2 (clan) 2]C^ possesses two intermo] ocular hydrogen bonds. Each clan molecule shows a hydrogen bond from N(l) to the 0(11) of another molecule. The other hydrogen on each N(l) is hydrogen bonded to the ionic chloride. Relevant hydrogen-bonding data for these two compounds are also presented in Table 17. o All intermolecular distances less then 3.6 A were calculated and carefully examined. No unusually short intermolecular distances were found. Ligand-induced proton shifts may be of biological significance. Since proton transfers in living systems are relatively comnon, the study presented here provides an important examination of orientation effects and enhanced stabilities which may be achieved by a small shift of one proton.

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CHAPTER 5 A NOVEL BINUCLEATING LIGAND: THE CRYSTT^ AND MOLECULAR STRUCTURES OF 1 , 4-DIHYDRAZINOPHTHALAZINEBIS (2-PYRIDINIUMCARBOXALDIMINE) NITRATE DIHYDllATE AND iJ-CHLGROTETRi^J'i.QUA [1 , 4-DIHYDRAZINOPHTHALAZINEBIS (2-PYRIDINECARBOXALDIMINE) ] DINICKEL(II) CHLORIDE DIHYDRATE Binuclear complexes of chelating ligands have been of interest recently for their potential activation of other 6 8~ 7 3 ligands at an accessible bridging site and for their magnetic properties. ^'*''^^~^° The structure of [Ni2C£{H20) ^. (dhphpy)]Cl^ shows the planar chelating ligand, dhphpy, to be capable of binding two metal atoms simultaneously. In that complex, a bridging site betv/een the nickel ions is occupied by a chloride ion. Therefore, at lea-st one bridging ligand in addition to dhphpy may be accommodated by M2dhphpy complexes. V7hile the study of magnetic interactions betv/een metal ions through bridging atoms in svxch systems is convenient and theoretically significant, the catalytic possibilities of this type system are exceptional. The nitrogenfixing enzyme nitrogenase has been considered to contain a polynuclear active •4. 6,7 site. ' Although the mechanism of the reduction of N2 to KH^ by nitrogenase is not understood N2 is believed to be coordinated to the metal ions of the enzyme. ' ' Nitrogenase has been shown to reduce a wide variety of small molecules 7 which contain a triple bon i , The distance betv/een the rt'etal 83

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84 ions should be of importance in the activation of tliose molecules. In the complexes of Robson and coworkers and of 8 3 Okawa et al . the metal-metal distance is essentially controlled by a single bridging phenoxide ion. However, in dhphpy complexes the metal ion separation is fixed at tx greater distance by the geometry of the chelating ligand. Therefore/ larger molecules which are reduced in the presence of nitrogenase, e.g. N^, N^; ^2^* ^2'^2' ^"^ HCN, should bo suitable for incorporation as bridging molecules opposite the N-IJ bridge of dhphpy. The syntheses and X-ray structures of H2dhphpy (NO^) 2-H20 and [Ni2C£ (H2O) ^ (dhphpy) ] Ci^, • 2H2O were undertaken to examine the nature of the accessible bridging site in coniplexes of this type ligand. So3.ution an d Re f inemen t of t h e Struct ure of H2dhphpy (N03)'2 • ^^2^ The direct method of syn^olic addition was ust-d in v;hich the signs of tv/o hundred large E's v.'ere assigned. All fourteen nonhydrogen atoms of the ligand within tlie asymmetric unit were located in an E-map computed from the signed K values. Two Fourier syntheses v.-ere used to validate the selected model, locate the remaining nonhydrogen atoms, and refine the atomic parameters. The refinement is outlined in Table 5. The observed and calculated structure factors are given in Table B-3. The final positional and thermal parameters are presented in Tables 22 and 23.

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85 CO CN o

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86 « N to

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87 Sol ution and Refinement of the Structure of [Ni2Ct:(H20 ) 4 (dhphpy) ]C£-:;-2H20 The position of Ni(l) was determined from a sharpened three-dimensional Patterson function. The positions of the remaining atoms were determined in a manner analogous to that used v;ith C^CoCH-dmg) (dmg) (clan) . After the hydrogen atoms were located they were included in further refinement with each having an isotropic thermal parameter one unit higher than the refined isotropic value for the atom to which the hydrogen atom v/as bonded. A sutrmary of the refinement is given in Table 5. The scattering factors for the nonhydrogen 29 atoms were from Hanson et a l . and the hydrogen scattering 30 factors from Stewart et al . Lists of observed arid calculated structure factors are given in Table B-4. The final positional and thermal param.sters are listed in Tables 24 and 25. Results and Discussion The atomic numbering and thermal ellipsoids of K2dhphpy" (N02)2*2H20 are shown in Figure 6 and those of [Ni2Cc(H20)^ (dhphpy) ]C£2*2H20 are shown in Figure 7. Selected interatomic distances of both compounds are listed in Table 26 and corresponding angles Z'-re given in Tables 27 and 28. Both compounds crystallize v;ith the cationic complexes, their anions, and water molecules linked in a three-dimensional hydrogenbonded network. The postulated hydrogen bonds in the structures are listed in Table 29. Diagrams illustrating the pack-

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88 Tabic 24 The Final Atomic Parameters^ of the Nonhydrogen Atoms for [Ui^Cl iU^O) 4 (dhphpy ) ] 0^3 . 2H2O Atom e 11 Ni(l)

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Table 24extended 89 22 33 '12 '13 23 273(4)

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90 Atom Table 24 continued y 2 '11 C(12)

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91 Table 24 extended continued ^22

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92 CQ vococccr. cof^oovorMvoinr-ion-^-^vokDin
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93 0) C! -H P C O O in rH rt N >^ a) o d +> P o O
PAGE 107

r^ A

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95 k-^

PAGE 109

rH rO

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97 mwm ) "

PAGE 111

98 o

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99 CN tN o-> fs] o cN n o^
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100 0) H EH nJ
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101 Table 28 Selected Angles in [Ni2C£ (H^O) ^ (dhphpy) ] C^^ • 2il Atom Angle Atom Angle N(l)-Ni(l)-C£(l) 98.0(2) N N(l)-Ni(l)-N(4) 76.8(2) N N(l)-Ni(l)-2vI(10) 155.7(2) N N(l)-Ni(l)-0(1) 91.1(2) K N(l)-Ni(l)~0(2) 90.3(2) N N(4)-Ni(l)-C^(l) 174. G(2) N N(4)-Ni(l)-N(10) 78.9(2) N N(4)-Ki(l)-0(1) 87.8(2) N M(4)-Ni(l)-0(2) 91.1(2) N N(10)-Ni(l)-C^(l) 106.3(2) N N(10)-Ni(l)-O(l) 88.5(2) N KM10)-Ni(l)-O(2) 89.6(2) N 0(1)-Ni(l)-Ci:(l) 90.9(2) 0(i)-Ni(l)-0(2) 178.0(2) 0(2)-Ni(l)-C£(l) 90.3(2) N(10)"C(11)"C(12) 122.2(7) N C(ll)-C(12)-C(13) 117.8(8) C C(12)-C(13)-C(14) 120.3(9) C C(13)-C(14)-C(15) 118.4(8) C C(14)-C(15)~N(10) 122.3(8) C C(15)-N(10)-C(ll) 119.1(7) C N(10)-C(ll)-C(10) 116.2(7) N C(12)-C(ll)-C(10) 121.6(7) C C(ll)-C(10)-N(4) 114.7(7) C C(10)-N(4)-N(3) 125.9(6) C N(4)-N(3)-C(l) 115.3(6) N N(l)-C(l)-N(3) 115.7(6) N C(2)-C(l)-N(3) 122.7(6) C N(l)-C(l)-C(2) 121.6(6) N C(l)-N(l)-N(2) 121.8(6) C C(l)-C(2)-C(7) 116.8(6) C 2)-Ni(2)-Ci(l) 97.8(2; 2)-Ni(2)-N(6) 76.5(2 2)~Ni(2)-N(20) 154.8(2: 2)-Ni(2)-0(3) 93.1(2: 2)--Ni (2)-0(4) 89.5(2: C)~Ui{2)~Cl{l) 174.1(2: 6)-Ni(2)-N(20) 78.2(2: 6)-Ni(2)-0(3) 90.4(2: 6)-Ni(2)-0(4) 91.2(2: 20)-lii{2]--Cl{l) 107.5(2; 20) --Ni (2) -0(3) 88.3(2; 20)-Ni(2)-O(C) 89.8(2; 3)-Mi(2)"Cf-(l) 88.2(2; 3)-Ni(2)-0('0 177.2(2; 4)-Ni(?)-C,C(3) 90.5(2; 20)-C(21)-C(22) 121.9(7 21)-C(22)-C(23) 118.7(7; 22)-C(23)-C(24) 120. 2(P' 23)-C(24)--C(r:5) 117.7(8; 24)-C(25)-K(20) 122.6(7 25)-N(20)-C(21) 118.8(6; 20) -C (21) -C (20) 116.7(6; 22)-C(21)-C(20) 121.4(7; 21)-C(20)-N(6) 113.8(6; 20)-N(6)-M(5) 123.4(6; 6)--N(5)-C(£) 113.8(51 2)-C(8)-N(5) 116.3(6; 7)--C(8)-M(5) 121.8(6; 2)-C(8)-C(7) 121.0(6; 8)~N(2)-N(1) 120.8(51 2)-C(7)-C(a) 117.0(6;

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102 Table 28 continued Atom Angle Atom Angle C(l)-C(2)-C(3) 123.5(6) C (6) -C (7 ) -C (8 ) 123.5(6) C(2)-C(3)-C(4) 119.7(7) C (5 ) -C ( G) -C (7 ) 119.4(G) C(3)-C(4)-C(5) 120.1(7) C (4 ) -C (5) -C (6 ) 121.6(7) Ni(l)-N(l)-N(2) 122.4(4) N.i (2 ) -N (2 ) -N (1) 123.3(4) Ni(l)-N(l)-C(l) 115.8(5) NJ.;2)-N(2)-C(8) 115.9(4) Ni(l)-N(4)~N(3) 115.9(4) Ni (2 ) -N (6) -N ( 5) 117.3(4) Ni(l)-N('l)-C(]0) 118.2(5) Ni(2)-N(6)-C(20) 119.1(5) Ni(l)-N(10)-C(ll) 111.9(1.) Ni(2)-H(20)-C(21) 112.1(5) Ni(l)-N(10)-C(15) 128.9(5) Ni (2) -N (20) -C (25) 129.1(5) Ni(l)-C£(l)-Ni(2) 98.4(1) The estimated standard devjations are given in parentheses,

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103 o

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104 ing and hydrogen bonding in Il2dhphpy (NO-^) 2* 2H2O and in [Ni2C£{Il20) 4 (dhphpy) )C£3-2H20 are presented in Figures 8 and 9. The most noticeable difference in the structures of the two dhphpy ligands is that H2dhphpy (NO-^) 2 * 2il20 contains a tv/ofold rotation axis while the nickel complex docs not. In both cases the ligand is approximately planar (see Table 30) . The nickel atoms and the bridging chloride of [hi.2Cl (II2O) ^(dhphpy) ]Cf o • 2H2O lie slightly "below" the least-squares plane of the ligand (Plane 3) and both hydrazone portions are pivoted generally about an N(3)---N(5) axis witli both C(14) and C(24) "above" the plane. However, in the protonated ligand one hydrazone is pivoted "upv,ard" and the other "downv/ard" as required by the twofold axis. Also, the hydrazone "arm5'. " in the nickel complex are drawn tov^ard each other compared to the pro tone'! ted form as indicated by the bond angles within the "arms." All of tl.e pyridine ringn are rotated about tlje C(nO)-C(nl) bond relative to the phthala^ine plane with the pyridine nitrogen atoms tipped toward the coordinated species. In [Ni2C£ (lUO) . (dhphpy) JCZ^21I2O the pyridine containing N(10) is rotated to a much greater extent than that containing N(20). This is shov/n by tho deviations from plane 4 (Table 30) of N(10) and C(12), 0.121 and 0.222 A, compared to the deviations of N(20) and C(22), 0.148 and o 0.161 A. The rings of the phthalazine fragment in each compound appear twisted relative to each other but by less than 2".

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n:l

PAGE 119

106

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Ui •H I ^ O u ... N N < >s >1 + >> CM ^<;\ P + to CN rH ^r> Pi M & = o — Ol (N ^d C --, fj ,i^ o >i M a, N X) ,a I ^\^ --re) •^ >i 0) ^ + )-> O f^i fO i rA -^ ^ l>i u , -'d rt! IX o <: fo a.

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108 E • o

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109 o 0) -Q o m CM o ^ a. .c c •H (0 0) C! a &< u to I 4J W Oj T.5 0) C Q nJ •H <-7 «0 OJ n O >1 a 1:5 n l-l p-1 o -p < CD o <; CM r--; 0) C rH O P < CM rH Q) c rH o -p < I I f-J r 4c IT! Cj I in I I CO u rH ro CM I rH rH CN o V.0 i:> ro r-l I o ro I l-~ VD ID C) u u CO t 4; ri f. C "I u t_) r?.; r-~ rH rH '-D
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110 en in

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1.11 All bonding distances involving nonhydrogen atoi/.s are normal. The N-N distances in both compounds range from o 1,363(7) to 1.374(4) A and are comparable to the N-N dis° 84 tance in 4-FPYTSC of 1.36b (3) A, Since, this distance in both the phthalazine and hydrazone groups is significantly shorter than the accepted N-N single bond distance, 1.44±4 ° 85 A, and since the ligand is planar, a delocal3.zed system is presumed to exist. In agreement with this assumption the C(nO)--N distances are longer than the pure C--N double bond distance and are all equivalent to the related C-N distance O O A in 4-FPYTSC, 1.275(3) A."" All other distances within the ligand are not significantly different from those in [Ni(dhph) (H^0)2C^^ -21120.^^ All Ni-N distances in [Ni^C-f. (H^O) ^ (dhphpy) ] Cf.32H2O are within the range of reported bonding distances of nickel (II) with aromatic nitrogen atoms (2.00 to 2,112 A). The bridging chloride is not symmetrically located between the two nickel atoms with Ni-'C-£ di.:;t3nces of 2.374(2) o and 2.387(2) A. The appearance of this bridge is remarkably similar to that in di-y-chlorosym trans -dichlorobis(2,9p o dimethyl-l,10-phenanthroline) dinickel (II) • 2 chloroform where the Ni-C distances are 2.378(3) and 2.394(3) A. Also, the Ni---Ni distance, 3.602(2) A, and Ni-cC-Ni angle, 98.0(1)°, o in that compound are equivalent to the 3.603(1) A separation and 98.36(7)° angle in [Ni2C£ (H2O) g (dhphpy) ] 0^3 • 2H2O. This distcince betv/een the nic}:el citoms is somewhat shorter than

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112 the 3.791(4) 7v distance found in the [Ni (dhph) (H2O2] 2C^4 * 2H,.0 complex reported by Andrew and Blake where both bridges are phthalazinc nitrogen atoms. The separation between the nickel atoms in the dhphpy complex, however, is o substantially longer then the Ni''-Ni distance of 2.879 A in the doubly oxo-bridged complex of Hoskins, Robson, and 7n Schaap. All these inter-nickel distances are much greater than tv;ice the covalei;t radius of nickel and must be a function of the bridging atomj. The distorted octahedral coordination geometry about each nickel atom in [Ni^Ci^ (1120) ^ (dhphpy) ] C>e32H2O is completed by two v:ater molecules which lie on a line almost perpendicular to the llgand plane. The Ni-0 bond distances are 87 typical for water coordinated to nickel (11) ranging from 2.070(G) to 2.117(G) A. A degree of uncertainty exists concerning the poiitJ.ons of hydrogen atoms abouL 0(1) in Il2dl]phpy (NO^) 2 * 2H2O. The o 0(1) -n(l) distance appears to be very short, 0.78 A, while o the N(10)-H(py) distance appears to be very long, 1.21 A. Although the locations presented for the hydrogen atoms are the most reasonable interpretation of the difference map in terms of rcrk heights, distances, and M-O-H angles, other areas of positive density exist about the N(l), 0(1) , and N(10) positions. Disorder may exist with alternate forms having N(l) protonated or having a "coordinated hydronium ion." Complexes of dhph:y structurally provide a promising

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113 uni-iuolecular system for the incorporation of a small molecule at a bridging position. Dinitrogen has been reported as a bridging ligand connecting two metal complexes in the y-dinitrogen-bis{ [1, 2-bis (dimethylphosphino) ethane] hydr ido[q(1/ 3, S-trimethylbenzene) jmolybdenum} cation ard similar 89 compounds. No complex has been reported which could retain its structural integrity after the removal of a bridging dinitrogen. The structures presented here suggest complexes of ligands similar to dhphpy may have such a capacity.

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CHAPTPjR 6 MODELS OF PROPOSED INTERMEDIATES FOR THE CATALYZED CYPT TZATION OF ACETYLENES: THE CKYST/iL AND MOLECULAP STRUCTUPFq OF l-(Tr-CYCL0PENTADIENYL)-l-TRIPHi^NYLPII0SPIiINE-2 3 ^ ^^"-'^^^^ TETRAKIS{PENTAFLU0R0PHENYL)C0RALT0LE AND 1(tt -CYCLOPFNTA DIENYL) -l-TRIPHENYLPIIOSPIJINE-2 ,3 , 4 , S-TETFJ^KIS (PENTAFLuiROPHENYL) RHODOLE The catalysis of tho oligornorization of acetylenes by tran.sition metal complexes has been extensively studied. ^^ A reaction mechanism involving a metallo-cyclopentadiene intermediate has been suggested^"^^ for the trimerization of two molecules of acetylene v^ith one of olefin in the prescencc of NiBr^Ctpp)^, Ni (CO) ^ (tpp) 3, and ether nicJ.el catalystF:. Metal-containing hererocycles, metallocycles, have been implicated^^" ^^"^^ as intermediates in the react: onr. of acetylenes v/ith Tr-cycIopentadienyJdicarbonyl-metal complexes in which the metal was cobalt, rhodium, or iridium. Yamazaki et_ea. on the bar.is of chemical reactions assigned a metallocyclic structure to a phosphine-containing cobalt complex isolated from the reaction of diphenylacetylene with Co(cp) (tpp)!^ and isopropylmagnesium bromide. They also isolated the same product from the reaction of excess diphenylacetylene with Co(cp) (tpp)^. A preliminary report of the structure of a cobaltacycle formed by the reaction of Co(cp) (tpp) (PhCiCCO^Me) with dimethyl maleate has been reported. 114

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115 15 Rausch and Gastmger prepared C. (f ph) .Co (cp) (tpp) by the reaction of bis (pentafluorophenyl) acetylene with r-cyclopentadienylcarbonyltriphenylphosphinecobalt. The analogous rhodium compound was prepared by the reaction of the corre15 spending rhodium compound. 9 7 Except for one preliminary report no structural data have been available for cobaltacyclopentadiene metallocycles. Therefore, the X-ray diffraction stjrucLural analysis of C. (fpii) 4C0 (cp) (tpp) v/as undertaken. The corresponding rhodacycle was studied for comparison with this cobaltacycle and related compounds. Structure Sol ution e md Refineva ent for C 4 (fph) 4Co"(cp) (tpp) ~ The heavy atom method was used in vjhich the positions of the cobalt and phosphorus atoip.s were estimated from a sharpened Patterson function. A Fourier synthesj.s based on these atoms v/as used to estimate the positions of eighteen additional atoms. Successive Fourier syntheses revealed the locations of all nonhydrogen atons in the c;ompound. A differ(Bnce Fourier synthesis at that point revealed a region between the cobaltacycles which v;as of relatively high electron density. Because this density v/as diffuse no additional atomic positions were estimated before starting refinement, R = 0.27. Three cycles of least-squares refinement with individual isotropic theriual parameters reduced R to O.l'l. A difference Fourier synthesis again revealed relatively high eloc-

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116 tron density in the same location as Lefore. Because of the discrepancy of the calculated density 3 3 (1.423 g/cm ) from the measured density (1.59 g/cm ), solvent molecules were presumed to be in the crystal. The deep red 14 crystals of the compound were grown from Skelly C which is a saturated hydrocarbon fraction boiling betv.'een 88 aiid 9 8°C and consisting mainly of n-heptane, ^-j^^i^' ^^ two solvent molecules were in the unit cell the calculated densiity would 3 be much nearer the measured value at 1.55 g/cm . Several maxima were observed in the difference Fourier synthesis v/ithin the region of high electron density. The distances between these points and the angles made by lines connecting them did not reasonably approximate a hydrocrirbon chain. The thermal parameters were converted to their anisotropic equivalent and nine least-squares cycles using a block approximation to the matrix reduced R to 0.077. The sliifts of all parameters during the fineil cycle were less than onetenth of their resi^cctivc estimated standard deviations. A difference Fourier synthesis calculated at this stage again suggested the presence of an ill-defined solvent molecule. Although the distribution of the peaks, which were not v;ell resolved, suggested a C-, oi' Cg chain, a closer examination of the distances and angles within the group shov.'cd them not to reasonably approximate a hydrocarbon chain. Six peaks were selected which closely retained their positions in the final ?'ourier summation before refinement and in the difference Fourier syntheses just discussed and

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117 which seemed the most reasonable in approximately a hydrocarbon chain. These locations were used isotropically as carbon atoms together with the seventy-three refined positions from the third full-matrix least-squares cycle used anisotropically in a structure factor calculation and in three cycles of block approximation least-squares refinement. Although almost all the poorly matched reflections (|FqV)^ ^Valc^'*^^^ ^^~ proved, a Fouiier synthesis revealed peaks at positions shifted to a less reasonable distribution from the linear hydrocarbon approximation used. The refinement was terminated at this point. An outline of the refinement is presented in TaDle 5. Scattering factors for cobalt, phosphorus, fluorine, 29 oxygon, and carbon v;cre taken from Hanson c t a ]. . A list of 14 observed and calculated structure factors is available. Structure Solution and Refi.neiuent for C4 { fph) 4lZh (cp) (tpp) The method of isomorphous replacement was used for the solution of the structure of C. (fph) ,Rh(cp) (tpp) . The cell constants of C^ (fph) .Co (cp) ( tpp) and C^ (fph) 4Rh(cp) (tpp) as reported in Table 4 are very similar with differences of less than one percent. The positional parameters from the third cycle of full-matrix least-squares refinement for trie nonhydrogen atoms in the isomorphous compound C. (fph) 4Co(cp) (tpp) were used in a structure factor calculation and a difference Fourier synthesis with the C^ (fph) ^P.h (cp) ( tpp) data. The structure factor calculation res\iltod in an R of 0.17 and the

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118 difference Fourier synthesis revealed no major structural differences in the tv;o compounds. The same positional parameters were used in an isotropic least-squares refinement of the C, (fph) ,Ill-i(cp) (tpp) data. A summary of further refinement is given in Table 5. A difference Fourier synthesis after refinement suggested the presence of an ill-defined solvent molecule. As in the 3 case of the" cobaltacycle the calculated density, 1.47S g/cm , 3 is significantly less than the density of 1.60 g/cm obtained from flotation measurements of the yellow crystals. If two molecules of n-heptane are assumed within the unit cell the 3 calculated density v;ould be 1.60 g/cm . An attempt to fit a linear molecule to peaks in the difference Fourier synthesis was also unsuccessful and was not pursued. The scattering factors used v.-ero taken from Hanrion 29 et al . Tlic observed and calculated structures are listed m Table B-5. Results and Disc u ssion for C4{fph) ^Co(cp) (tpp) and C4 (f ph) 4Rh (cp) (tpp) The. final positional and thermal parameters for the. nonhydrogen atoms of both C. (f ph) .Co{cp) (tpp) and C^(fph)^Rl-i(cp) (tpp) are listed in Table 31. The atonic numbering and thermal ellipsoids of the cobaltacycle are shown in Figure 10. The atomic numbering of the rhodacycle is analogous. Selected bond distances and angles for the two compounds are listed

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119 1

PAGE 133

120 CO

PAGE 134

121 CM ca

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122 ca CQ CM CQ >-. N 00 00 c— I CT* o o ro 'T m "^ cr\ i-H r~r^ vd vd CM IT) f-{ o rr^ vD in in r^ OS in O i-{ in n CTl rH in in CM in in v£) 00 00 cH rH rH r-. in t— in T rH o rH rH r-\ rH vr in •-t r-l in V.O n P-) O rH rH t-A ^^ O rH rr~ rH r-l rH rH CTl CT\ VD in VD VD CO rVD in o in in •<3' r~t -^ VD CD 00 o rVD CTv VD O CM O CTl rH rH vf o. en CN m

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123

PAGE 137

124

PAGE 138

ca Ti B u 4J d 0) •H 0) 4J -P •iH o (i) > to C 5^ O X! ^ in +J -P O u o 0/ o d d (& 'J 4J Q) o m 00 D^ — d U •H M "-d d t-i (ti fci o u 0) ^ ^ o o a) y^ ' ,d — p -a* a o -. x; o XI w -P a, trs w «n d "> r^i — -H >i o x; 1T3 o ^ -^ d -d w u n -d w Eh a; o c "d o to r-i O 0) . -d d o x: -p •H

PAGE 139

126

PAGE 140

127 in Tables 32 and 33. Least-squares planes and deviations are given in Table 34. The molecules are metallocycles with the metal atom also bonded to the cyc]opentadienyl ring and to the triphenylphosphine ligand. The C(l) to C{4) fragment in both compounds is planar with the largest deviation from the best plane being 0.015 A in the cobalt compound and 0.017 A m the rhodium compound. The metal atoms, however, are significantly displaced from the plane in the direction of the cp ring by -0.203 and -0.239 A. This perpendicular displacement is simi9 8 lar to that found in other similar metallocycles. The metallocycles may be considered as a dolocalized diena with the metal atom a-bonded to the two carbon atoms of the ring, C(l) and C(4). The Co-C bond distances, 1.995 (11) and 1.993(11) A, and the Rh-C bond distances, 2.060(12) and 2.067(11) A, are similar to various values given by Churchill. ^^ Values of 1.979(1) A"''^ and 1.990(5) A^ have more recently been reported for Co~C bonds in ccbaloxime complexes. Mague '^"'^'^ has reported structures of similar rhodacyles in which the Rh-C distances are 2.000(11), 1.964 (11), 2.047(16), and 1.998(16) A. Also, Cotton and Norman o report a singi.e-bcnd covalent radius of 1.39 A for Rh(ITI). When this value is added to half the 1.485 A suggested length for a single-bond between sp carbon atoms the Rh-C diso tance is predicted to be 2.13 A. The observed Rh-C distances where rhodiuj.i has a formal oxidation number of ^•l are shorter than r.he abc/e prodicted single-bond distance. T'ais iliffer-

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128 Talkie 32 Selected Bond Distances (A) of C^ (f ph)^M(cp)(tpp) (M=Co,Rh) with Their Estimated Standard Deviations in Parentheses. M = Co Rh M-C(l) 1.995(11) 2.060(12) M-C(4) 1.993(11) 2.067(11) H-P 2.234(3) 2.293(2) M-C(51) 2.157(12) 2.286(13) M-C(52) 2.121(13) 2.261(14) M-C(53) 2.119(11) 2.250(13) M-C(54) 2.104(9) 2.238(10) M-C(55) 2.133(12) 2.268(12) C(l)-C(2) 1.326(15) 1.343(16) C(2)-C(3) 1.467(16) 1.457(16) C(3)-C(4) 1.335(15) • 1.354(15) C(l)-C(ll) 1.487(16) 1.498(17) C(2)-C(21) 1.523(16) 1.497(16) C(3)-C(31) 1.481(15) 1.478(16) C(4)-C(41) 1.493(16) 1.492(17) P-C(60) 1.848(11) 1.858(12) P-C(70) 1.843(11) 1.821(10) P-C(80) 1.834(12) 1.820(13) C(51)-C(52) 1.463(20) 1.429(22) C(52)-C(53) 1.400(15) 1.420(17) C(53)-C(54) 1.426(18) 1.424(20) C(54)-C(55) 1.433(16) 1.422(17) C(55)-C(51) 1.457(17) 1.431(18)

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129 Table 33 Selected Bond Angles (°) of C4 (fph) 4M (cp) (tpp) with Their Estimated Standard Deviations Given in Parentheses. (M=Co,Rh) M = Co Rh M-C(l)-C(2) 112.1(8) 115.5(8) C(l)-C(2)-C(3) 116.8(9) 114.9(9) C(2)-C(3)-C(4) 114.8(9) 115.5(9) M-C(4)-C(3) 113.1(7) 114,8(8) C(l)-M-C(4) 82.4(4) 78.3(4) P-M-C(l) 103.0(3) 101.6(3) P-M-C(4) 95.2(3) 93.3(3) C(ll)-C(l)-M 127.0(7) 123.3(8) C(ll)-C(l)-C(2) 119.6(9) 119.4(10) C(21)-C(2)-C(l) 123.9(9) 124.1(10) C(21)-C(2)-C(3) 119.2(9) 120.9(9) C(31)-C(3)-C(2) 119.7(9) 119.7(9) C(31)-C(3)-C(4) 125.5(5) 124.9(10) C(41)-C(4)-C(3) 119.8(9) 120.3(9) C(41)-C(4)-M 127.0(7) 124.9(7) C(51)-C(52)-C(53) 108.1(11) 108.3(12) C(52)-C(53)-C(54) 109.6(10) 108.8(11) C(53)-C(54)-C(55) 107.7(10) 106.9(11) C(54)-C(55)-C(51) 108.0(10) 109.3(11) C(55)-C(51)-C(52) 106.3(10) 106.8(11)

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130 Table 34 Deviations from and Equations of Some Lease-Squares Planes of C4(fph)^Co{cp) (tpp) and C^ (fph) ^Rh (cp) (tpp) .^ ° +3 (a) Deviations {h x 10 ) Atom

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131 ence could be indicative of multiple bonding between the terminal carbon atoms of the diene and the metal atom. The C-C distances in the metallocycle rings fall into tv/o groups. The C(l)-C(2) and C(3)-C(4) distances are equal within experimental error to the accepted value of 1.337(6) h for a simple C-C double bond. The C(2)-C(3) distances are indicative of a C-C single bond between tv.-o double bonds. The observations of Mague ' on tvi/o rhodacycles suggested a doublebond system similar to those in C^ (fph) ^Co (cp) (tpp) and C^ (fph)4Rh(cp) (tpp) . The cp rings in the compounds arc planar v;ith the maximum deviations from the least-squares planes of -0.016 o and -0.012 A. The distances from the cp ring atoms to the metal atom shov/ that the metal atom is slightly displaced from the center of the cp ring. The range of the Co-C(cp ring) distances is from 2.104(9) to 2.157(12) A v;ith a mean of 2.127 o (9) A. These values are similar to those in other Co-cp complexes. ^05,106 In both the cobalt and rhodium compounds the longest metal-C(cp ring) distance involves C(51), the carbon atom nearest the phosphine ligand. The mean Rh-C(cp ring) distance o is 2.286(13) A. This value is equivalent to the mean distance of 2.246(9) A in Rh (C2F5) (cp) I (CO) "^^"^ and falls within the o 2.19 to 2.26 A range reported for corresponding mean values for other cprhodium complexes. The C--C bond distances v/ithin the cp rings range from 1.400(16) to 1.463(20) A with a mean of 1.436(11) A in the

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132 cobalt, compound and a range from 1.420(17) to 1.431(18) A o with a mean of 1.4 25 A in the rhodium compound. These C-C distances are comparable to those found in other cp complexes. ' The cp rings are tipped relative to the C(l) to C(4) planes by 35.3^ and 36.6°. o The Co-P distance of 2.234(3) A is similar to the Co-P distance in five-coordinate complexes of cobalt where the no ^ range is reported " to be from 2.152(G) to 2.27(1) A. Also, in cobalt-carbonyl complexes such as Co^ (CO) • « (Ph2PCiCCB'2) 2 and Co(CO) -;,(N0) (tpp) the Co-P distances are 2,236 and 2.229 A-'--'--' Jn the former and 2.224(3) and 2.230(3) A-*"""-^ in the latter. The Rli-P distance of 2.293(3) A is similar to those in 113 phosphine complexes of rhodiura(I) . ' The metal to phosphine distance in metal-oxime complexes have been found to be some40 97 v/hat longer, ' The Co-P distance in cobaloximc complexes has been reported as 2.327(4) h^^ and 2.339(1) A.^^ The PJi-P ° 102 distance in RliC-£loxes in both cobalt and rhodium are equivalent, the phosphorus atom may be in the position of closest approach to the metal atom as limited by the steric constraints of the oxime ligands. The distances in the fph rings have been summarized in Table 35. The individual values for the distances and angles in the fph rings on the metallocycles and the phenyl rings of the phosphides are given in Tables 36-38. The dimensions are not unusual and are in agreement with expected values.

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133 -p D4 o< -G

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134 Table 36 Bond Distances and Bond Angles of Pentaf luorophenyl Groups in C^ (fph)^Rh(cp) (tpp) . o (a) Distances (A) n = 1 2 3 4 Cnl-Cn2 1.384(15) 1.342(16) 1.392(15) 1.385(15) Cn2-Cn3 1.364(20) 1.400(20) 1.374(20) 1.351(20) Cn3-Cn4 1.375(18) 1.358(18) 1.357(19) 1.389(18) Cn4-Cn5 1.367(19) 1.365(20) 1.368(18) 1.355(19) Cn5-Cn6 X. 372(20) 1.373(19) 1.367(18) 1.362(19) CnC-Cnl 1.393(15) 1.389(14) 1.389(16) 1.386(14) Cn2-Fn2 1.347(12) 1.354(12) 1.351(13) 1.344(12) Cn3-Fn3 1.339(15) 1.341(18) 1.349(15) 1.348(16) Cn4-Fn4 1.338(18) 1.337(19) 1.335(18) 1.340(18) Cn5-Fn5 1.343(15) 1.358(14) 1.338(15) 1.357(14) Cn6-Fn6 1.331(13) 1.343(14) 1.351(13) 1.342(13) (b) Angles (°) Cnl-Cn2-Cn3 123.1(11) 122.4(12) 123.7(11) 122.9(11) Cn2-Cn3-Cn4 119.6(13) 119.3(13) 113.8(13) 120.2(13) Cn3-Cn4-Cn5 119.6(13) 119.3(14) 120.8(13) 117.9(13) Cn4-Cn5-Cn6 119.8(13) 120.6(13) 119.0(12) 121.4(12) Cn5-Cn6-Cnl 122.6(12) 121.1(11) 123.6(11) 122.0(11) Cn6-Cnl-Cn2 115.3(11) 117.3(11) 114.1(10) 115.4(10) Cn -Cnl-Cn2 124.2(10) 123.9(10) 123.1(10) 124.1(10) Cn -Cnl-Cn6 120.5(10) 118.8(10) 122.5(10) 120.5(10) Fn2-Cn2-Cnl 120.2(10) 121.3(11) 118.2(10) 119.4(10) Fn2-Cn2-Cn3 116.7(11) 116.4(11) 118.0(11) 117.7(11) Fn3-Cn3-Cn2 120.9(12) 120.7(13) 120.3(12) 120.8(12) Fn3-Cn3-Cn4 119.5(12) 120.0(13) 120.9(12) 119.0(12) Fn4-Cn4-Cn3 120.7(13) 121.3(14) 119.9(13) 119.9(12) Fn4-Cn4-Cn5 119.7(13) 119.4(13) 119.3(13) 122.1(13) Fn5-Cn5-Cn4 120.9(13) 120.1(13) 119.6(12) 118.8(12)

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135 Table 36 continued n = 1 2 3 Fn6-Cn6-Cn5 115.7(10) 118.3(11) 117.6(10) 117.2(9) Fn6-Cn6-Cnl 120.4(10) 118.8(10) 118.5(10) 119.7(9)

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136 Table 37 Bond Distances and Bond Angles of Pentaf luorophenyl Groups in C^{fph)^Co(cp) (tpp) . e (a) Distances (A) n = 1 2 3 4 Cnl-Cn2 1.387(14) 1.372(16) 1.394(14) 1.403(15) Cn2-Cn3 1.388(19) 1.368(20) 1.398(19) 1.358(19) Cn3-Cn4 1.387(17) 1.374(18) 1.370(18) 1.348(16) Cn4-Cn5 1.382(17) 1.374(20) 1.372(18) 1.370(17) Cn5-CnC 1.382(18) 1.363(13) 1.362(18) 1.384(17) CnG-Cnl 1.385(14) 1.389(14) 1.408(15) 1.367(14) Cn2-Fn2 1.322(11) 1.341(12) 1.339(13) 1.358(11) Cn3-rn3 1.350(14) 1.338(17) 1.339(14) 1.338(14) Cn4-Fn4 1.360(17) 1.339(19) 1.334(17) 1.335(16) Cn5-Fn5 1.336(13) 1.354(13) 1.330(14) 1.361(13) Cn6-Fn6 1.341(12) 1.355(13) 1.356(12) 1.348(12) (b) Angles (°) Cnl-Cn2-Cn3 122.4(11) 122.9(12) 123.4(11) 122.6(10) Cn2-Cn3"Cn4 119.7(12) 119.2(13) 118.9(12) 120.5(12) Cn3-Cn4-Cn5 119.6(12) 120.1(14) 120.2(13) 118.7(12) Cn4-Cn5-Cn6 118.7(12) 119.0(12) 119.8(12) 120.4(11) Cn5-Cn6-Cnl 123.9(11) 122.9(11) 123.8(11) 123.0(10) Cn6-Cnl-Cn2 115.6(10) 116.0(10) 113.9(10) 114.5(10) Cn -Cnl-Cn2 123.3(10) 123.8(10) 122.9(9) 124.2(9) Cn -Cnl-Cn6 121.0(10) 120.2(10) 123.0(9) 121.3(9) Fn2-Cn2-Cnl 121.4(10) 120.5(10) 119.1(10) 119.8(9) Fn2-Cp2-Cn3 116.2(10) 116.6(11) 117.5(10) 117.7(10) Fn3-Cn3-Cn3 120.4(11) 122,0(13) 119.9(11) 119.1(11) Fn3-Cn3-Cn4 119.9(11) 118.8(13) 121.2(12) 120.4(11) Fn4-Cn4-Cn3 120.0(12) 121.2(13) 118.9(12) 120.1(11) Fn4-Cn4-Cn5 120.4(12) 113.7(13) 120.9(12) 121.2(11) Fn5-Cn5-Cn4 119.7(11) 120.5(12) 119.9(12) 119.8(11) Fn5-Cn5-Cn6 121.6(11) 120.5(12) 120.3(11) 119.8(10)

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Table 37 continued n = 1 2 3 137 Fn5-Cn5-Cn6 119.4 (12) 119.3(12) 121.4(12) 119.8(11) Fn6-Cn6-Cn5 117.7(11) 115.0(1.1) 117.6(11) 117.9(10) Fn6-Cn6-Cnl 119.7(11) 119.9(10) 118.9(10) 120.1(10)

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138 a D4 o <4-l U C •H H ^^ CO x: fo Cu CO i C (U J^ •H u O W at en c < C O m 'd c en o c (0 -p (A a 'd c o CO 0) o (0 4J CO •H D (0 r-Pi vr> O x: o u ^ « o u 11 fO

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139 in in in Ul CO CO

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140 The fluorinated mctallocycles resist thermal decomposition better than the hydrocarbon analogs. ' Enhanced thermal stabilities have been observed in other highly fluorina114 ted metallocycles relative to their hydrocarbon analogs. In the compounds of this study the triphenylphosphine ligand and the four fph rings provide an effective shield for the two double bonds in the metallocycles. Although the fluorine atoms of the fph rings and the phenyl rings of the tpp were omitted from Figure 10, the sterically hindered nature of the metallocycle may easily be seen. The lack of a convenient path for an attacking acetylene together v/ith the enhanced thermal stability of the fluorinated derivatives may have allowed the isolation of these intermediate metallocycles. Metallocycles of cobalt and rhodium of the type presented are reasonable intermediates in the catalyzed oligomerization of acetylenes.

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CHAPTER 7 CONCLUDING REMARKS The structure of C^Co (H2dmg) (drag) (clan) shows the same LIPS phenomenon as c£ Co (H^dtag) (dmg) (sulfa) /'^ These two compounds exhibit the unusual feature of containing both neutral and dianionic dimethylglyoxime groups. Also, the orientation of the benzene ring of the sulfa and clan group in the respective compounds is over the dianionic dmg. The various distances and the relative orientation of the axial ligand in both compounds suggest a n-type interaction. LIPS supports the contention that "hydrophobic forces" are important in enzymic processes.^ The bis (diglyoxima to) cobalt (III) complexes of aniline derivatives have here been shown to be useful models for the examination of tliis type interaction. An extension of X-ray structural determinations to similar compounds with other aniline derivatives and with other diglyoximes is suggested. Lowtemperature X-ray studies could effect better resolution of the inter-drug bridge structure and the N-0 distances . An investigation of the fluorescence spectra of these compounds could reveal additional information concerning the interaction between the equatorial and axial ligands. The fluorescence of 5-dimethylaminonaphthalene-l-sulfonamide was observed to be enhanced while the fluorescence of carbonic 141

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142 anhydrasG was diminished when a 1:1 complex of the tv/o was formed. "* Although the major contribution to this observation is believed to be the ionization of the sulfonamide, a portion of the change is attributed to a hydrophobic interaction. -''' ^^^ The fluorescence spectra of cobaloxime complexes with aniline derivatives should help reveal tlie nature of the interligand interaction as a function of the orientation angle. The novel ligand dhphpy has been demonstrated as a binucleating ligand. The bridging site occupied by a chlorine atom in [Ni2C£ (H2O) ^ (dhphpy) ] Cf^ clearly is accessible and of convenient dimensions to accommodate a molecule such as dinitrogen. Further development of this system as a possible model for nitrogenase should include use of molybdenum salts and work with the exclusion of oxygen. Synthesis of similar ligands with saturated "side arms" is also suggested. The compounds C^ (f ph) ^Co(cp) (tpp) and C^ (fph) ^Rh (cp) (tpp) contain a butadiene fragment with each end bound to a metal atom. The metal to carbon bonds are shorter than expected for the single-bonded distance. The metallocycles are, therefore, believed to contain a delocalized Ti-bonding system. While metallocycles should be higl;ly susceptible to nucleophilic attack and thermal decomposition the two compounds studied here are very stable. The enhancement of thermal stability by the fluorinated substituents may be at least partially responsible. Also, the presence of the four fph rings

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143 along with the tpp and cp ligands provides a shield from attack for the metallocycle. The understanding of catalytic processes should improve the efficiency of our existence. Hopefully, enzymic processes occurring in nature can be duplicated in the laboratory by suitable models. These model enzyme systems may then be applied to cure the diseased and feed the hungry.

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APPENDIX A BOOTH I Tl A listing of the FORTRAN language computer program BOOTHITl follows. This program was designed to interpolate atomic positional parameters by Booth's method from the values of a Fourier synthesis calculation. The Fourier synthesis program v/ritten by Dr. Gus J. Palenik v;as modified to store the calculated values on a magnetic disk. After supplying BOOTHITl with input data of the approximate position of each atom, the stored values are retrieved. The program estimates the position of maximum electron density for each atom from these Fourier synthesis values. The positional parameters may be translated to equivalent positions and may be passed to a bond distance and angle program. The resulting fractional coordinates are punched into IBM cards in the format required for their input into the Fourier synthesis and least-squares refinement programs. 144

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145 »

PAGE 159

146

PAGE 160

147

PAGE 161

148

PAGE 162

149 n n 3 n 3) n n a rj > z V X 0^ r, --~ z c o •• j:— — •ULL <~ U. U. ID -C O D «» 0". O rjcG •-CI— i_ riiiz • _j< 2: -•jjxl — OZ— II z ^hZ — — -AJ — M_ o X a tz + > M z z + + -^ z z og ^^ je I+ -> z z •a 01

PAGE 163

150

PAGE 164

151

PAGE 165

152 a o o > 2 in > » J L' > J 0. z L + -. J > II I H c< • ^ _l > II (.0 I •< • > • — u. L. — -^ *s '» ~ -< J + I lj_ J. '^ J • '^ »— »-^ *-4 9 ^.. »-* »-^ _J _' _l >» > _! * • in v, a a -. (\i a a _l V) u. (/) u. a II _j II -J II >i II II •X ^ a. a 7. J z a z a

PAGE 166

153 iD

PAGE 167

APPENDIX B OBSERVED AND CALCULATED STRUCTURE FACTORS

PAGE 168

Table B~l Observed and Calculated Structure Factors for c£Co (H2dpg2) (clan) •C2H^0H

PAGE 169

15C FCI rc FC FC f c FC I O FC H=

PAGE 170

157 FO FC FO FC ro FC -1

PAGE 171

158 1 2 3 A t) 6 V 9 10 1 1 12 -li -12 -1 1 -10 -9 -8 -/ -C ~ _ c. _ -4 -1 H= 1 3 4 5 t) 7 e s 13 1 1 -1 1 10 -y -t -7 -C — c-4 H= 1 '1 1 l't3 1 'it 2H2 14J ?0^ 2V<* i';3 1 'I -5 1 *•1 ^.V 1 tb I '. 1 '.0 1'. 1'. o l^fc 147 J '«a 1 i. t1 , K•137 -l'»0 -1 ( 370 31 3 l'*9 -143 -143 1 •'( S WiB 1'. C ) b:i ic 1 -14 5 -1 60 2oe 300 -139 209 -13ti j 1 'j -1 4 7 8 -L -7 -6 -b -4 -1 H= 1 3d 142 1 f V 267 1'. 3 13S 144 140 14b 146 14 7 Ibl 1'. a 2 1 y 14 3 14fc 1 13 146 30 4 143 -1 bO 1U.3 -1 bl 242 FC 106 -bO -3 -1 231 e7 145 •2PP 1 74 129 -190 4 2 114 -22 1 7 3 -34 -147 105 -3 23 4 166 -36 9 -cn 4 1 I 1 1 97 125 -SO -?7C lit* -142 -89 33 -1 8 -23 ie3 132 GO 277 -2 27 -36 3 IC6 24 -39 -139 -4? 1 03 12 174 97 -38 ie.9 7e -143 191 20 19 126 bb ^7 -2 06 -38 13 -4b C-6 157 -16 4 -4 -3 -2 1 y-~ 2 t, 6 O 10 1? 14 1 6 18 -20 -1»^ -16 -14 -1 2 -10 -8 -6 -4 1 2 3 4 b 6 7 8 9 10 1 1 la 13 1 'I 15 16 1 7 If 19 -19 -IP -17 -16 -15 -14 -13 -12 -1 1 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 FO 1 4 9 2 3 4 14 « -lb) -14b b9 2 ^^? 113 1 189/5 1 724 7-) 6 24 6 -137 56. i 4cit> I 4 3 -136 bb7 b4 4 -i 4 372 4 6' 91. 6 1 1 2 6 rc 138 84 -29 -bO -79 569 -916 1113 1823 lt97 7 / 2 7 2 125 ^60 46 I 1 3 1 -156 565 -626 £39 -46 3 -3/8 444 -Sb7 10/3 K314 1 00 1 529 209 I 2 55 1 1 ;. 306 3i;7 359 -114 38 2 4 1 7 42 6 336 50 '•l 1 3 • -13 9 -13-. -136 -146 -1 3H 350 2<'0 24 I 24 5 -13^ -12 J 33 1 1 3 62 3 58 1 138 5 602 38 4 1273 180 bi.'8 -98 309 1 53 1525 -231 1271 -58 -258 380 -322 2 373 -4 14 -435 34 6 555 161 -340 38 -4 1 89 -55 -373 170 235 -22 5 121 -j'2 -292 29 6 19 -583 -1377 £91 399 -1239 78 -491 -272 29 C 7 8
PAGE 172

159 FO FC FO FC FO FC FO FC

PAGE 173

160 to FC f-0 FC rc FC FO FC 1 7 -

PAGE 174

161 L

PAGE 175

162 L

PAGE 176

163 L

PAGE 177

164 FO FC FU r c FC FC FO FC 1 1

PAGE 178

165 L

PAGE 179

166 FCl FC FO FC 10 fC FO FC s

PAGE 180

167 FO FC FO FC FO FC FO FC 1 z

PAGE 181

168 rv re FC »-c f c f c ru FC v

PAGE 182

169 L

PAGE 183

170 r u re KU FC » O FC f O FC -13

PAGE 184

171 FC PC FO rc FC FC FO FC -2

PAGE 185

Table B-2 Observed and Calculated Structure Factors for [Co(Hdnig)2(clan)2]c£

PAGE 186

173 FO FC FO f C FO rc FO FC

PAGE 187

174 FO FC FO fC ro rc i (I rc

PAGE 188

175 FO rc FO f-C FO FC ro FC -4

PAGE 189

176 L

PAGE 190

177 FO rc FO FC r o f-c ro FC 2

PAGE 191

178 ru FC FO FC HO FC f O FC », «,

PAGE 192

379 L

PAGE 193

Table B-3 Observed and Calculated Structure Factors for H^dhphpy (NO^) ^

PAGE 194

181 n= e e 10 h-6 e 10 2 .4 6 e 10 1-:= C ?. A 6 e 10 H= p. 6 H= HPO 0, K 32 1 1 01; >: 9 2 37 2, K = PA 7 26 9f. 73 FC 3?3 !C0 ?63 -?ft2 -?'i 1 ??? ?? 77 KC e e 6 3M 130 ?6 1C.9 9 6, b31 13 1 -J 8 SB -22 e. K 29 6;.<5u3 &0 AC :?q7 3i". I r:.c. sets i;= 10: K = b't 2 3?/j 4 239 6 Ab e -2 i 09 6P -2 39 C 1 A . i: -1 a -1 9 22? 79 r.-';0 i;25 1 26 30 14 -r9y f-3 ^3 -41 3?5 ??9 -*. 5 10 ?3 4 C2 -5A I 233 -e? 16, K = 2 2 I Oh -2 1 -21 IP. K = It.V bl -22 1 ^2 -16 3 2 FO 20. K: 32 «22 FC 20 85 -21?, K=
PAGE 195

182 f D rc f o PC FC rc (a f c 7

PAGE 196

183 H= H= H= H= 1 2 3 4 FCI G. KFC FO PC FO FC 1

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184 A 5 7 B V 10 FO 407 H7 3 'J -20 97 FC ACA 3C) -?0 90 H = K = i 2 3 t) 6 7 8 9 10 361 33? 1 L.t. !<' 1 J (. t. 1 I '' 3e 79 -20 -20 40 3'.) 5 320 166 I 17 It? 1 1 ? -30 7 'J ?1 A9 K = 1 2 3 4 b 6 7 8 9 1 19 429 t>ti 1 AO 70 3 A 233 31 51 3C. 112 4 2 '3 67 1 40 7 6 -16 -2A0 -23 -48 -32 H= K = 1 2 3 4 6 b 7 e 9 H= 1 2 3 4 5 6 7 e l6Ci 79 102 m 117 57 b3 124 -2 I 48 O. K bAO 2i>'> 16 122 I e 134 58 30 94 4 b C 7 1 2 3 4 r o -21 -20 -21 62 10 lb -B -53 14, K = 102 61 1 1 1 63 -21 -21 -22 91 -61 -107 Ol -7 -2 -10 4 b 6 7 8 9 10 y1 ? 3 4 H1 2 3 H^ H= 16, K-2 1 -21 -2 1 -21 68 18, K.= -21 -2) 'i -23 2 . '---23 -2 0. <= -170 -01 -103 -00 121 56 -43 129 20 -51 1 2 3 4 5 46 1 1 1 162 -23 42 -3 37 -21 -17 71 I I -4 43 20 -1 1 23 no 161 36 H= 1 tj , «.= 3 4 5 6 7 6 9 10 FO _lo 30 132 13'. 282 225 / 1 -21 4 3 -10. »2 66 113 75 2 1 eo -20 62 £21 -21 -22 10 -40 129 142 294 23 6 69 -2 -30 -263 -16-* -66 10 -e4 20 66 -219 28 20 1 2 4 5 6 7 e 9 10 -8. K = 37 107 63 -I 7 C2 165 65 275 1.17 48 --36 1C9 -^•6 -26 59 171 -7 7 -2V6 -125 -49 H= -e, K-536 -253 -5 u e 10 141 -53 25 99 3 4 5 6 7 33 -22 -22 240 -22 46 46 H= -16. H= »0^ K = 1 2 3 4 5 6 7 8 -21 33 6 8 203 256 6 3 35 -23 -40 18 17 -240 1 1 43 54 22 39 -68 -209 -26 1 -5C -38 12 6 7 e 9 10 42 1 173 2J;3 16 e2 -li.^ 40 56 -22 141 1 2 3 4 5 6 7 8 9 10 FO 1 12 165 k 10 52 i!08 212 101 -20 66 -21 FC 106 lb 7 llO 51 206 -209 -94 -4 60 1 H = KH= 1 2 3 4 5 6 7 8 9 10 202 661 275 30 3 1 55 53 125 -21 169 1 2 3 4 5 6 7 8 I 45 U>1 1 t, 19 19 48 64 -2 I 36 1 46 174 2 -1 1 33 -69 -3 30 H= -2 H1 4 K.= H= I? K1 2 3 4 5 6 7 e 9 32 -19 1 10 -20 -21 299 42 52 44 1 2 3 2 7 34 17 1 54 -16 31 173 55 H= •12 3t> 37 7 1 1 '> -2 -17 304 -49 -57 -47 4 27 1 2 3 4 5 6 7 8 9 10 112 15 2^4 62 44 -18 4 2 62 68 36 1 2 3 4 5 6 7 9 50 79 2AU 1 CO 2 60 225 65 -19 -20 -21 H= 412 -169 2A5 10 -90 -3 45 -59 -28 13'. -201 -66 5 277 29 -27 58 -92 -126 25 171 -113 38 -241 63 -4 2 47 -59 -90 41 1 2 3 4 5 6 7 e 9 56 46 -16 167 72 89 39 98 58 50 -66 24 3 98 2r.7 -226 68 14 16 1 47 -63 6 167 -74 -89 29 97 57 44 HK-1 2 3 4 c 6 7 8 123 40 4 6 53 41 56 71 97 -21 125 -38 -40 56 -42 -6 1 -64 98 -21 F = K = 1 3 4 5 6 7 8 53 233 169 -19 47 71 -21 66 44 -235 -165 -47 -72 15 62 -1 1 11 K = 1 2 3 4 5 6 7 1 6 157 31 -20 -20 2,7 31 -21 165 155 -27 lA -13 -36 -6 26 h= 13. K = 1 , K= 5 149 -138 I 2 3 -20 87 79 87 28 -86 73 91

PAGE 198

185 4 5 6 1 2 3 A 5 FO 1 1 '. -21 -2 1 H= 1 2 3 H= 1 J5, 37 -? I 1 1 4 6^1 -22 -22 IV, K -21 -22 -21 '>3 1^. K -23 -22 K = H= -19, 1 2 3 A 5 37 131 1H3 -2? '23 FC 1 15 1 107 i-g 1 -31 -?5 52 5 30 -V -21 1 19 -179 9 ?0 FO FC -17, 1

PAGE 199

186 ro re H= 1

PAGE 200

187 FO FC FO FC FO FC FO FC 2

PAGE 201

188 H= M = 1

PAGE 202

Table B-4 jlated Stri. (dhphpy) ]Cl^'2E^0 Observed and Calculated Structure Factors for [Ni,c€ (H„0) .2 2 4

PAGE 203

190 L

PAGE 204

191 FO FC FU FC FO FC FU FC -7

PAGE 205

192 FO FC FC FO FC FO FC 10

PAGE 206

193 FO FC FO FC FO FC FO FC -13

PAGE 207

194 FO FC FO ^C FO rc FO FC 24

PAGE 208

195 FO PC FU FC FO FC FO FC -Ifi

PAGE 209

196 FO FC FO rc FO FC FO FC 20 27 2b ?b 2 4 23 22 21

PAGE 210

197 FO FC FO FC FO FC FO FC

PAGE 211

198 L

PAGE 212

199 L

PAGE 213

200 — 1> -A -J 1 Mt o 43 4 5 6 7 d 9 10 1 1 13 14 -2 6 -.?0 -ii4 -23 -22 -21 -20 -\<^ -Hi -1 / 16 -15 -i 4 -13 -12 -1 1 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 FO 331 423 24« 200 211 7, K = b30 -tu 701 -81 1C9 -80 283 443 -81 -80 233 -82 -83 2i.6 -80 129 21 8 481 106 231 4 70 382 219 128 1 18 28'^ 228 Ibl -80 143 224 428 225 b3 7 3 72 708 617 377 1 84 7 77 -80 FC -348 4 08 -7 38 -243 197 -222 -62 5 1 6 -88? t.8 1 8 9 39 2 9 4 -4-j>0 84 -24 -2 4 4 -72 6 227 33 -81 235 4 99 -148 215 -'4 5 3 -397 227 153 -52 ? 8 '» 21 9 1 8 2 -93 1 17 212 4 3 7 1 'VI 5 4 4 - J 264 321 59 7 64 14 9 7 1 41 -60 341 -95 -33 32 -301 4 65 4o2 -51 Z7 17 -344 155 -225 -42 6 150 -2o0 1 1 3 225 317 I 1 5 ~7 ) -3f.8 -7 13, K-85 -87 -8o 190 -85 146 -85 1 5o -85 24 6 -87 -87 -38 -8? 420 K = 1132 732 -72 4 I 5 82 1 5a 442 335 38 4 1 * I 5 2 U 30 a I d 9 ,^^Z 1 1 / TO 1 22 -72 -1 73 -30 1 54 20 97 59 21 1 20 -45 -94 1 35 -4 Oo 10 -1196 7 75 -1 3 95 823 -15 1 -44 3 M-o -334 1 t^d 5 3t> 3"/c -1 Ou 22 3 -y3 15 lu 1 7 IQ 19 20 21 2 2 H1 2 3 4 5 6 7 8 9 10 1 1 12 1 3 14 15 16 1 7 18 19 2 -2 3 -2 I -20 -19 lb -17 -lo -15 -14 -1.3 -12 -1 I -10 -9 -8 -7 -6 -5 4 -3 -2 1 FO 171 -81 36^; 182 48 I -33 -84 2 33 2, K:: -72 220 402 744 326 21 9 317 -79 -78 492 2iJ 456 3 79 -62 204 <; 7 J -3 2 454 218 -30 4') 6 1 55 341 226 44 I 1 65 158 428 -81 55 5 2 56 -78 490 4 84 438 640 l<>6 1 4 5 561 322 2 55 7 5 3 377 302 H: FC 1 71 I 02 -37 8 -190 -4 30 -20 22 -24 6 1 81 21 4 41 -7 51 3.51 -I 6 9 90 -3 4 72 321 442 -333 47 21 3 -4 33 -437 233 103 -452 1 3 6 3 4 9 202 4'»3 21 1 -212 -'»34 o -606 262 9 503 4 9 J -4 39 639 -191 1 46 DOO -34 9 -253 -760 -3 9 1 3 J9 K1 2 3 4 5 6 7 3 9 10 1 1 1 2 13 14 1 5 1 6 1 7 •2a -23 695 461 344 435 538 -79 261 41 4 395 3D1 400 27 7 -ill 257 1311 295 -04 21 8 233 422 10 71 9 -473 -397 -51 1 52 250 4 33 401 2 93 -4 02 -283 -I 09 -250 1 58 -276 1 I 200 -233 4 19 -22 -21 -dO -I 9 -1 8 I 7 16 I 5 14 -13 -12 I 1 10 -9 -8 -7 -6 -5 -• -3 -2 I HFO 2.4 3 200 -82 5'yO -80 65 199 -80 2 40 361 334 471 653 -77 7b 20 4 2-.>3 -75 01 6 -75 2 1 7 539 H = K =

PAGE 214

201 FO FC FO FC = o FC FO = C 1 1

PAGE 215

202 FO FC Fl) FC F O FC FO FC 1 1

PAGE 216

203 FO FC FO FC FO FC FO FC -3

PAGE 217

Table B-5 Observed and Calculated Structure Factors for C^ (fph) ^Rh (cp) (tpp)

PAGE 218

205 FO FC H= K = 1 Jr 3 4 5 6 7 8 9 10 1 1 12 13 14 15 16 17 -21 1C97 67 1 21 3 o -172 53 6 234 — ^ <* "^ -173 K1 2 3 4 5 6 7 6 9 IC 1 1 12 13 14 15 16 -18 -17 -16 -15 -14 -13 -12 1 1 -10 -9 -8 -7 -6 -5 -4 -3 -2 -I 164 4 155 30 1 1 179 332 I 2a9 128 53 7 3&9 254 41 -63 427 120 2S2 — ^, *! 22 5 -C7 153 192 -6 9 3:) 3 -53 432 123 t20 331 257 63 1 308 S"J9 IC2 50d 1102 552 1 -2456 -Bl -1 5 4 1 cr4 -259 1 r63 -loe 51 9 423 -?48 -423 -6 403 134 -2G3 1 237 -9 17 4 107 -90 -375 -52 4 '5 134 -84 2 -304 250 CO 7 235 -91 5 -36 553 I 44 9 -G50 K = 1 2 4 5 6 7 8 9 10 1 1 1? 13 14 15 -19 797 4 4't 61 1 12«t3 157 114 7 7 7 3-^8 3e.a 24 3 329 -66 323 -6/ 301 -70 104 195 -363 -772 -1260 223 1 1C7 14 -37 5 -344 252 3 34 -30 -317 3 6 30 1 38 86 18 17 -IC 15 I 4 -1 3 -12 -! 1 -10 -9 -r> -7 -6 -5 -4 -3 -2 1 FO 177 -65 190 187 172 -61 617 5^ 1 4 60 313 52 2 1415 -b^ 1607 353 -45 920 1C6 FC 173 22 -191 183 157 -6 -62 1 -50 4 453 299 -537 14 9 3 -53 1629 42V 18'-' -518 154 K= 1 2 3 4 5 6 7 8 9 10 1 1 1 2 13 14 -19 -18 -17 -1 6 15 -14 -13 -1? -11 -10 -9 -8 -7 -C -5 -4 -3 -2 -1 1 047 30 7 559 46 4 1 ' 9 27-55 2t7 -62 21 I 33 -69 2 93 -69 130 2 4 4 3). 1 35 7 -66 23 V 1 53 1 16 l'*0 3 c?. -54 196 2 20 369 163 964 254 9-i9 1 16 I 1 45 H= 1 2 3 4 5 6 7 9 10 II 12 13 20 -19 -18 -17 -16 -15 -57 286 59 1 624 62b 122 456 14 1 -t>t> 165 26 358 104 150 390 -66 414 -64 -OJ 14 -13 -12 1 1 10 -9 -6 -7 -6 -5 -4 — 3 -2 -1 FO 223 374 410 4S6 176 409 21 7 238 160 1 1 C2 838 550 682 -57 1".= 699 26 525 442 1 86 2 18 279 104 • !97 -338 85 29 6 -o4 128 -243 -3i<1 363 9 4 -232 146 -89 145 406 -1 54 -201 201 32 2 -210 I 035 -223 -776 253 -997 -64 307 -6 1 -6 19 3 28 6 0-O -103 -4 8 8 -112 6 153 26 1 -35? -125 — 138 384 2 -407 -18 71 1 2 6 e ic :i 12 -20 -19 -16 17 -16 15 14 -13 -12 1 i 10 -9 -8 -7 — 6 5 -4 -3 — 2 1 FC 336 348 -4 02 5 1 5 180 431 2C6 -262 -226 1 C6 8 897 -5C9 -613 25 K2 53 337 6 48 993 301 46C 167 235 165 543 305 135 238 il > iS 423 218 184 222 1 8 862 720 <;4 4 87 341 470 41 7 efc2 1307 1 195 130 4 1 8 I 2 -^ 4 5 6 7 8 9 10 1 1 20 • 19 18 17 16 1 5 14 13 1 2 1 1 -I -9 -8 1 16 3£5 IBB 2 15 1 69 355 I'lS 213 192 132 -7 1 -72 -67 177 139 163 £27 -11 5 279 1 3S 330 693 ?9'-. ZC9 34 7 -371 646 9 86 -269 -475 165 223 151 15t'305 1 6 -V 252 5t> -307 -52 428 237 J75 -228 96 852 74 1 122 4 7 7 -323 4 6 '1 J4l -722 13C6 1 156 165 4 75 1108 379 -178 -2iO U>9 357 129 -212 -205 147 98 -S8 -66 177 147 -191 -C3e -124 283 l^fa -344 -63 61 SG9 21 1 -7 -6 -5 -4 -3 -2 1 FO 4 61 526 -56 '56 567 90 470 1 2 3 4 5 e 7 8 9 -2 1 -20 -19 -18 -17 -16 -15 -14 -13 -12 -1 I -10 -9 -8 -7 -6 — 5 -4 -3 -2 -1 H1 2 4 5 6 7 8 -2 1 -20 -19 18 -17 -16 -15 -14 -1 3 -12 -1 I 1 C -9 — 8 -7 -6 -5 -4 -1 h= 590 105 6 6 -66 -67 252 173 244 1 13 205 242 -67 93 -64 -i>5 4 52 217 395 1 8 300 44 1 145 ^38 370 176 1 02 330 -54 134 326 275 FC -489 -544 4 5 -6 -56 6 -415 -603 -107 4 1 5 -6 1 -24 1 lol 249 132 -U'8 23 7 81 -86 -7 1 -4 1 4-')9 216 -389 -188 309 415 -14 9 -453 -381 199 41 -33 7 -20 1 28 367 292 K230 242 -67 -7 1^;0 262 -70 21 4 108 326 -68 -&7 173 -68 4Cl -65 /»m5 24 7 148 425 194 464 1 16 541 300 573 390 -60 799 145 235 24 1 57 -94 -1 18 2c9 73 -24 5 -72 -325 -1G3 60 16/ 146 -380 -7 455 ^32 -176 -4 14 206 474 -83 -546 -295 55 7 39 2 -22 -323 -142 K= 444 — 4 4 9

PAGE 219

206 I o PC FO fC ro FC I o FC 1 ? 3 4 b 6 -?C jy -It) -17 -16 -lb -14

PAGE 220

207 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 H= 1 2 3 4 5 6 7 8 9 10 11 -21 -20 -19 -18 -17 -16 -IS lA 13 12 -1 1 -10 -9 -6 -7 -6 -5 -4 -3 -2 -1 FO 940 27b -i.4 50b ?. a t. «Jb2 74 S t53 16& 77 1 FC P94 -65 -4 54 -214 icri 7f.t5 -7P7 49 -69 9 1 . K = 1 2 3 4 C 6 7 8 9 10 -21 -20 19 -18 -17 -16 -15 -14 -13 -12 -1 1 -10 -9 -8 -7 -6 -5 -4 530 ISO 73b 136 1 1 ? -63 -66 22'; 129 34 1 152 l£^0 24C -69 326 122 -65 156 -61 573 1K3 46 4 1C5 747 666 415 337 424 1 191 643 41 I 319 3'5fa 1 . K = 422 438 204 12{. 134 -68 -68 234 1 I 9 -71 -7 1 261 -6B 2?e 1 1 a 25^ 202 274 43 A 25b Ibl 28-;» 57 2 44 2 217 2 1 a o9C 42 3 109 -518 174 703 130 -llf. -35 57 24 1 129 -334 -156 169 23 42 -326 159 6 4 17? -1 7 -562 164 470 171 -750 -691 -379 -3) 9 -372 -I 149 — 549 400 243 361 430 433 -203 100 151 79 -5 -217 125 87 66 -276 -97 245 98 -238 -21 1 269 436 235 -205 -287 567 442 174 -2C8 -f 52 4 t 5 131 -3 -1 1 2 3 4 5 6 7 8 -21 -?:? -to -10 -17 -16 -15 -14 -13 -1 2 -1 1 -10 -9 -8 -7 -6 -5 — 4 -3 -2 -1 H= 1 2 3 4 5 6 7 -21 -20 -19 -1 8 -17 -16 -15 -14 -13 -12 -1 1 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 H= 1 2 3 4 5 -21 FO 9 3 7C4 -55 1 FC 1C2 730 34 K = 552 141 -66 -t.U -68 254 -6 9 237 -73 254 -6 5 152 -64 27 7 432 1 84 507 85 -57 149 -55 797 89 779 97 594 169 -56 550 -59 1 -550 -14 6 6 1 102 19 -255 -14 2 24 1 249 -67 -143 2 271 44 ! 196 -516 -83 67 167 54 -809 57 800 4 1 -604 166 87 54 7 K-66 2 54 -70 33 1 102 185 -70 175 172 155 31.18 539 3o3 399 194 236 254 160 310 31 1 758 206 4 6»V 138 31 1 236 173 433 107 1 t r. 490 -69 302 193 -71 21 1 98 14 2oa 71 — 53 J 47 212 6 3 1 6 3 -lf.5 160 33 334 -356 -385 201 262 23" -14.4 -315 328 770 -186 -51 1 1 16 2v3 240 -177 -436 -96 -514 30 302 208 79 -193 87 -20 19 18 1 7 -16 -15 -14 13 -12 1 1 10 -9 -6 -7 -6 -5 -4 -3 -2 -1 1 2 3 20 19 -18 -17 16 15 -14 13 12 -11 10 -9 -8 -7 -6 -5 -4 ^ "2 1 -20 19 -18 -17 -16 -15 1'. -1 3 -12 11 -10 -9 -e -7 -6 -5 -4 -3 -2 -1 H= -19 -la -17 FO -67 267 :;71 4 1 6 307 496 3Z:i -C5 1 42 4 56 1 ! 1 4 60 346 602 -63 -65 355 4£ 1 2 9'.' 2 04 164 -70 127 179 -67 135 104 396 169 1 73 £02 3 20 2 39 2 64 i<:£ 224 134 239 2 68 1C6 IVO 2 34 276 -71 1 • X 177 -74 129 2 7 -66 -67 122 zco 317 -66 32 2 183 2 '.4 1 3 3 -69 2C5 194 27 1 250 -67 153 -69 FC -J7 -279 •388 4 1 5 299 -50 1 -icy 136 466 -102 -4 30 351 6C4 33 30 4 4f; 2C8 -3C7 10 168 1 02 100 -200 -79 141 102 -4 16 192 169 529 337 -2o5 -259 216 228 -100 -282 -277 92 177 -242 -258 -79 1 1 -156 103 152 -199 -96 -40 144 221 -3 05 -<.-7 336 230 266 -141 -49 199 179 -280 -2'*8 10 144 50 -16 15 -14 -13 1 2 -I 1 10 -9 -8 -7 -6 -5 -4 -3 -2 h-17 -16 -15 -14 -1 3 12 1 1 -10 -9 -8 -7 -6 -5 H= -13 1 2 -1 1 H5 6 7 8 9 1 1 1 12 13 14 15 3 4 5 6 7 a 9 iC 1 I 12 1 3 14 li 16 17 FO 222 -65 216 177 2 58 2 1 -67 139 14/ 138 292 206 1 33 -70 109 I K = -68 180 -68 258 177 202 185 -<;9 100 -70 246 179 1 83 I, ^ -74 24 7 -71 -70 20 6 -69 217 187 -68 188 1 19 219 130 2 05 137 -67 282 -66 ''i 6 -63 Ob 66 122 -63 1 69 224 135 1 02 149 -o8 FC -227 -24 21 1 156 -26 b -207 47 149 167 -123 -301 209 121 -15 -14 2 13 72 202 66 -269 -173 207 193 -13 -89 -63 23 7 175 -187 14 93 2 7 5 -71 = -14 68 — 194 -49 21 1 185 -15 -169 -133 208 134 -177 -13 154 -3 -274 10 91 40 -26 86 -114 18 1 53 -213 -132 124 1^7 2 2 K= 252 127 ISl 12 256 163 -173 1 2 3 4 1 10 -66 315 -66 359 K-12 93 -53 -3^1 21 361

PAGE 221

208 ro FC f o re FO rc ro FC 5

PAGE 222

209 FO FC -A -54 -77 -3 b9V ess -2 479 -CO? -1 I2:i7 -£70 H= K: -2 923 IC?! 1 DO 2 ?3« ? 689 -fi2e 3 292 -334 4 793 C?3 5 6S.d 75 J 6 69 9 -^4 7 7->.5 -f93 e 190 151 9 i:.fit> f:68 10 20 1 PC 7 11 <.99 -701 1? 29 7 -?'J.9 13 106 -1?? 14 2 2 ?C *? l.£. 2b4 ?4e IC -66 -1 17 -6 5 -A9 1 e 7 1 12 16 165 -13'^ -15 134 Iti<. -14 231 250 -13 -613 7 1 2 131 i I 4 -11 -62 V2 -10 56 1 56.4 -9 16« I£0 -a 475 -479 -7 914 -93<: -6 119 129 -5 143.'^ 13GH -4 201 -20* -3 1 120 I i:ji -2 lOt.3 P-S'l -1 142 72<^ 1. K= -1 794 -:'7.S 1 1464 lli;5 2 1)22 ?eft 3 6 7 -ire 4 911 61 1 5 97 -9C4 6 1006 ^7a 7 1S5U l«i5 6 7 6 e^ 9 54 -r-eo 10 -56 -ei 11 300 3?fi 12 20 2i»3 13 lie. 1 -'• 7 14 460 -4t-e 15 -69 JO 16 24 •; 23 17 14 3 I'^C: -17 27 5 ?A 1 6 15 9 It? -15 2 74 -?'.>', 1 4 117 I .: '"i -13 22 1 P.l-c -12 -f C 22 -11 162 -170 -10 2a3 -270 -9 34 -3':.-3 -3 121 - 1 24 7 6 B6 2 -632 7 S99 -57 3 a 2e6 289 9 195 184 10 -63 69 11 2i<6 -273 12 269 -266 13 S61 581 l.'» 207 314 15 -uG -bS -19 -j9 56 I -ft / 2 9 -17 193 -204 1 6 -<6& 9 -15 63 619 -14 2 94 2«0 -13 -&1 25 -1? 212 "192 -II 65 75 J Se 3 9 11 -9 aV-3 B4 7 -8 93S -94 3 -7 5<>2 -569 -6 3X0 319. -5 075 -766 -4 lO". 135 -3 l^^O -61.'i -2 2t2 -558 1 1120 909 2« K= 1 GO 126 1 lieO 9 69 2 -5Ii 27 3 *i»7 -3J2 4 734 -781 5 J!63 -406 6 1C2^^ 1029 7 ^®3 236 4 0/ 4 1 2 9 27.6 -267 10 ISJ -134 11 zap. Zhl 12 191 164 13 33sf -30 6 14 l-£9 -109 -1? tifo -1S9 1 3 I "J* 1 ' : -17 ^37 440 -16 167 176 -15 377 -37 -14 2J>4-255 -13 -S9 -i)5 -12 Jsiit 375 -11 -5.3. 7 7 -10 Si3 -S5« -9 3-59 -364 -8 *5.2 >i31 -7 aff'i -6-iO -6 S3i 93 -5 'J'il -04/ -4 2112-* -1952 -3 ?51 595 -2 1 IV^834 -.1 lT4
PAGE 223

210 9 -no -19 IH 1/ -It-1 b -13 -li; 1 J 10 -9 -0 -7 -6 -5 -4 -3 -2 -1 H1 2 3 4 5 6 7 -? 1 -20 -19 -16 17 -16 15 -lA 1 3 I?. -1 I -10 -9 -8 -7 -6 -5 -4 -3 -?. 1 K= 1 2 3 4 5 -?l -i'O -19 -1 6 17 16 li> -12 2f.H by. 129 AJb 2i;3 bC-.5 231 yu7 2ol 136 161 416 2^.9 r c 1<3P 19P leo 14 1 I'fU 3•J^ 2K4 617 1 14 -437 ?1 ."4 5 664 ?'» 3 •V04 -23C' e.?6 -10 1 -"".JO -2? 4 K = b'. 4 -6 8 16i5 121 152 1 09 -71 26b 140 -66 -6 4 -Oi> £';3 339 34 9 44b -60 440 230 406 222 89 9 30 b 1 3b -b7 344 29 7 44 1 64 -530 -•50 182 10 7 142 -1H9 89 259 125 -31 93 -B5 301 36 2 -366 -470 31 439 236 -421 -20? f.7 1 :o6 -146 -31 -323 206 473 37 K= 207 1?3 126 99 lb4 250 -6/ 1 '>( -t 'j -L.'i 47 7 237 -65 1 t4 100 30t. 3*1 4r> J 131 2? 9 343 21 8 'J6 138 -34 139 239 -63 91 27 48 -4f 3 -?4? 4 1 160 130 -315 -34 P 4'i 7 174 -320 -6 -5 -4 3 -? -1 H1 2 3 4 -21 -:-'0 -19 -in -17 -16 1 5 -14 1 3 -\? -1 I -10 -9 -8 -7 — 6 -5 -4 -3 -2 -1 MI ? -21 -20 -19 -1 P. 17 16 -lb -14 -13 -12 -1 1 10 -9 -8 -7 -6 -S 4 -3 -? -1 H = -20 -19 -\a -I 7 -16 -1 5 -I 4 -13 -12 -1 X -10 -9 -8 FO 361 100 b^2 334 4t>J 1 3b r c -34U 127 5V0 -Jo? -4 62 130 K = 278 -69 131 1 04 lOB -60 106 109 -Ol i:'b 3V4 -06 -Ob 324 195 4 7b 1 3r 44 4 332 312 4 16 104 390 144 453 -272 37 1 03 1 13 -U,7 -3'J -94 1 t'. 4 bo 51b -101 -361 -74 1 7 333 I'OO -4C2 -152 445 3.-^2 308 -421 --31 3d r> 15? -Ai;) J K= 1 20? 71 120 -08 -o7 2o7 1 92 292 102 22e 3o2 99 2 72 24b 257 26d 1 83 26o 120 22b 1 C6 -oy 3 7* -69 K= -69 393 130 6 •:> 103 99 237 -L.6 449 -06 173 -oO 134 191 53 -123 -30 -59 26/ 177 -29 b 1 I 2s2 377 58 -2ol -24 1 Za2 2bl -159 -270 100 2^'6 96 -60 -3oa 1 1 1 -5 -39 3 144 40 I 17 -103 -23 472 30 -214 26 144 -7 -6 -5 — c. -3 -2 -1 H= 18 1 7 16 -1 b -14 13 12 -1 1 -1 -9 -e -7 "6 -5 -4 H = 16 -l-» 13 12 -I ) -10 -9 -6 H = 7 e 9 10 1 1 12 13 14 lb H = 1 2 3 4 c e 7 6 9 1 1 1 1.' 1 3 14 I 5 I'j 17 FO ?01 -6H 4 32 1C2 2?0 104 71 — f •; 1 i! -) -6i. 229 -69 ?. 04 1 4 1 — ^^| '* 1 t .) ('J 2 £3 -7? 3f 2 -72 KFC -42 -442 -103 206 12b -O !• 1 2 67 -93 1C9 42 2^a 103 191 -163 ir> 1 ov f;b 262 Ul 3J3 93 1 3 ro rc 1 4 3 1 ?: 1 '"•! .. t C) K.3 -71 rrt ~ !d K 2 ; 9 /o 220 -67 196 225 -69 34 7 -67 2 by -67 193 lbf< -66 -lf>6 4 4 18t> 22 -64 -94 -6 -14 237 -bO -^03 b 194 220 -4 b -J3d -103 251 -2 166 H= -60 1 1 1 1 t 2 143 ISb -66 1 39 147 123 169 -t.4 31 1 -6b 160 -6b -70 197 -6 7 133 Ibo K= -13 -25 9f. 1 t,b 12o -I9f. -2 9 146 162 1 1 3 -201 -3t> 30b 166 64 129 197 16 = -12 152 -171 2

PAGE 224

211 FO FC FO FC FO FC FO FC

PAGE 225

212 FO FC FO fC FO FC ru re -10 -9 ~l> -7 -6 -h -< -3 1 2 -1

PAGE 226

213 FO FC FO FC FO FC FO FC -5

PAGE 227

214 HO FC -?

PAGE 228

215 -18 -17 -1 6 15 -14 -13 -12 1 1 -10 -9 -6 -7 -6 -5 -A -3 -2 -1 FO -65 IVl O i.1< 3;>7 4'< 1 t,7 6 -bt 5^9 £.P4 03 3 1307 63 5 0?9 2'-ie ICVO 1 '2 3 4 5 6 7 8 y 10 -21 -20 -19 -lb 17 -16 -IS -lA 13 -12 -1 1 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 162 -1.7 /;'J9 144 ^53 -05 31 i' 276 171 179 -69 151 26 I 151 -65 103 102 420 -60 439 412 436 6 1 30 7 6^7 3a3 673 905 149 59 370 tJ09 FC -9P -210 5 e9 42^ 154 -4?0 849 652 4 -5:15 -4yy 694 1 266 -605 -607 333 994 4 2 452 175 -262 -21 204 279 151 -1D5 4 133 -254 -133 79 126 -2 30 -425 -20 44 4 430 -400 -61 2 4 29 636 372 -936 -668 129 55 7 -335 -tiSl 1 2 3 4 5 6 7 9 -2 1 -20 19 -18 -17 -16 -15 14 -13 -12 -11 -10 44 5 333 ^•9 275 269 169 1' B 26 7 191 126 -6'3 163 9 7 -0?. 231 143 490 -60 t2 7 243 155 465 429 3~5 27 202 ?^S 200 1 '. ? -3 06 195 14 1 -29 173 -82 6 -236 -116 483 ?6 -6 56 -246 1 5 6 488 FO 419 404 1 01 1 356 02 5 101 353 51 5 1 14 HFC 436 -389 -140 12 H 4 6 3.i -10? -352 -5 37 119 K1 2 3 4 5 6 7 -21 -20 -19 -1 8 -17 -16 -15 -14 -13 -12 -11 -10 -9 -O -7 -6 -5 — /; -3 -2 — 1 \^ 1 2 3 4 5 6 -22 -2 1 -20 -19 -18 -17 -16 -15 -14 -13 -I 2 -I ! 10 -9 -8 -7 -6 -5 -4 -3 _ -» -1 384 376 160 -y8 305 16 1 358 2 :5 -67 2 55 146 -65 320 -64 27 5 93 4 62 276 -57 472 124 533 — 5o 687 324 354 1 87 261 486 -375 380 1 C i -7 -317 1 54 35-^ 249 -6 J -24? ' 44 64 30 7 23 -297 41 477 27 25 -475 128 550 91. -688 -329 ~^' 3 192 24 2 -4S< K = 240 3 66 223 -67 253 -69 273 225 -68 183 leo 139 227 212 225 -63 314 152 96 553 -59 497 277 209 -61 91 277 -65 490 219 -3 64 -203 63 26 7 34 -253 -22 3 -d3 190 19'J 127 -2 34 -228 229 34 -304 -167 72 5L.3 76 -463 -28B -230 -9 -8 -264 100 473 2 3 4 21 20 -!. 9 It -17 16 -15 -14 -13 1 i-1 1 ••10 "9 -7 -4 1 2 -21 -10 19 -18 17 -16 -15 1 4 -13 12 : 1 ic -9 -8 -7 -6 -A -3 -1 H= FO 22^ -70 2 09 -c r 1 1 50 -65 3 17 3:^5 2 14 -66 -63 2 66 -03 513 -62 23i -64 -6 5 -(5 208 c27 /I 456 < t '; 69 129 2 iO 2:8 i:.'7 2 36 -66 333 -'i50 100 221 -68 3 74 1 ^5 tCti 103 -67 -66 1 15 268 2 36 -69 -68 -68 FC 23 •4 (.> -271 6<< ->i7 -142 -25 389 :<2 3 -22 6 10 1 -3'^ 263 49 -514 -7 236 33 34 27 ma 624 54 -469 8 57 -ICC -275 -164 134 239 34 -333 -439 -60 226 1 18 -372 162 529 74 -55 -43 121 27 7 -257 -74 27 36 H= K176 -68 177 108 -21 -20 -19 la 17 -1 6 -15 14 13 -12 -1 1 10 -9 -8 -7 — ^> ^ c -il -3 -?. 1 H4. K = 102 379 -68 267 -66 -65 -68 154 116 2':;5 9fci 201 168 -o7 330 -4 9 3C4 22/ -70 257 4. K = -79 360 -19 -244 65 227 -33 -102 -128 -119 298 -8 -2ij7 175 62 32 1 16 -313 -66 219 -79 -226 10 -20 -19 •-i ^ -17 16 -15 -14 -1 3 -12 1 1 -1 — 9 -a -7 -6 -5 -4 -3 -2 ^,-18 -17 -16 -15 -14 -13 -12 -1 1 -10 -9 -B -7 — 6 -5 H = -16 15 -1 4 -1 3 -12 -1 1 -10 e,7 8 9 10 2 3 4 5 6 7 8 9 10 1 1 12 1 3 14 1 2 3 4 FU 1 03 '1 51 -68 316 -e.6 234 239 -66 210 -06 -67 -67 1 06 212 1 18 370 -70 230 -71 4, r.= -68 149 -6 8 193 191 166 169 -65 154 -69 142 160 -73 2 05 4, K--69 258 -73 178 167 1 12 158 4, K= 1 15 152 123 139 rc 1 09 163 -78 -34 7 -93 241 252 -59 -21o 9 95 63 -ir.9 -22 6 14 6 393 -4 6 -22 6 -14 1 1 C I r 4 7 1 -22 2 -183 170 152 -40 175 136 164 125 -207 12 -32 2u7 1 17 -14 5 -2C0 -.75 174 -15 ICO -J 45 -126 125 K= -14 -70 17o 173 146 231 1 03 103 175 168 171 203 1^9 -68 K= 141 275 -66 253 -66 -!C4 198 165 -157 -233 -92 1 13 160 -163 -175 1P3 139 -43 -13 131 30 7 -43 244

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217 FO VC FO FC FO FC ro re 1?.

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218 FO FC PU FC ' 14

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219 L

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220 ro re FO FC FO FC FO » C

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221 15 -9 -8 -7 -6 -5 - -6 1 27 7 166 24 9 130 i^^y 104 -6A 30 6 30 9 307 31 5 190 138 -69 155 -66 13 5 209 -65 337 -06 460 3Qb I 2 3 4 5 6 7 8 9 10 1 1 12 13 11 15 12 -1 1 -10 -9 -S -7 -6 -4 -3 -2 -1 K= 105 Iv 1 6 -31 -Ue 257 1 1 5 151 -104 -14 29 1 -31 1 3 6 162 154 57 149 ~3'i -127 -2oa -25 330 -70 -479 -384 8 2'>7 4'. 3 2 57 73 1 -60 429 19 4 -to 2 72 132 545 -64 461 1< 4 159 167 -70 230 -6 9 269 -65 -65 26 7 113 44 9 141 3C4 290 -232 -45 1 26 1 726 ?2 -402 182 21 235 130 -571 28 460 136 -l.?7 196 -52 231 _q^ -273 -46 P3 264 H4 -4t>0 M6 35 2 295 K = 1 ^ 3 4 192 657 155 4f)l 126 -7 203 6^6 146 -51 2 93 6 7 8 9 10 1 1 I? I 3 14 15 -13 -12 -1 1 -10 -9 -8 -7 -6 -5 -l 7 rc 326 94 -79 -604 -162 528 -6 -38t) -178 69 176 2S0 -13 -363 24 5 237 150 -1 1 -39 7 -220 131 22 -31 2 -300 -6 -4tl -155 -34 414 75 -412 -2 200 -36 -403 -174 248 2o4 39 -41 -272 196 ZJ i -J 1 :9 -103 -253 -67 550 26 -387 -153 o4 2 440 K = 1 2 3 4 5 6 7 o 9 n 1 1 \2 1 3 14 15 -1 ^ -13 -12 1 53 3«9 177 6tJ3 2b0 54 9 2tJ6 -f. I 335 14V 4<»0 1 /3 1 1 / 1 70 -t)6 12-. 1 72 3bo 121 -5 1 19 4 • 1 B3 •66V* 2SO 531 30 1 6 -37 7 149 436 175 -133 -179 -77 -133 165 36 3 -123 1 1 -10 -9 -8 -7 -6 -5 -4 -3 -2 1 FO 240 Ao 1 -65 295 7 1 2 t£5 3 5a 569 361 309 321 H= 1 2 3 4 5 7 e 9 1 1 1 12 13 -17 16 1 5 14 -1 3 12 -1 1 -10 -9 -6 -7 -6 -5 -4 -3 -2 -1 y.FC -251 -501 -103 2CJ -642 -689 301 520 34 -23 7 -329 FO FC K= 1 76 3c2 -54 221 286 2 10 4 68 92 5C6 1C8 4 06 -64 -67 232 "70 1 18 1C5 215 2^6 11:9 -64 399 5C7 527 212 233 -52 -52 -52 1 2 6 7 e 9 10 11 12 13 -17 16 15 -14 -13 12 -1 I -10 -9 -b -7 -6 -5 -4 -3 -2 -4 -192 -336 -88 235 305 -212 -457 46 507 -91 -407 -66 78 235 -96 l2o 66 -21 1 -237 -171 39 412 -37 5 -31 7 540 586 153 -277 -53 81 -2 K= -3 244 4 45 482 456 775 216 779 34 9 227 267 109 218 134 «24 1 1 1 219 251 172 130 221 88 215 444 183 614 173 1 14 310 220 705 270 436 4f -.^54 -757 212 767 -364 -204 273 lOB 212 -9 5 403 1! 2 -216 -259 204 166 203 -43 -238 4 25 173 -530 -127 1 8 238 235 -CU3 -1 1 2 3 4 S 6 7 a 9 10 1 1 12 -18 I 7 16 -1 5 -14 13 12 1 1 -10 -9 -O -7 -6 -5 -4 -3 — 2 -1 880 -857 6 c r,.161 555 544 342 550 21 2 343 -65 -(.7 229 -65 253 -69 177 258 220 360 291 -64 -63 4 32 355 -55 -5'i -53 -52 257 738 103 -51 385 H= n1 2 3 4 5 6 7 9 10 1 1 19 •18 -17 16 -15 -14 -13 -12 -1 1 -10 -9 -3 -7 -6 5 -4 -3 -2 -1 286 10 14 553 -59 -to 23 1 3t^3 -65 408 177 122 -7 1 97 102 245 1 05 -65 145 1 1'3 3C5 4 04 540 49 3 9 13 -53 4 lo -52 467 3J1 402 49cS -2 16 1 -54 1 -513 34 2 54 6 -214 -336 50 -60 -26 -24 4 18 -175 -274 239 37 1 -259 -8. -127 447 355 -32 -1 12 106 -10 -253 -695 -956 -; 1 37 4 _ 1 30 97t> 535 -95 19 206 333 25 -3*^9 104 1 17 108 -78 126 24 2 -107 -51 lo9 106 301 -3'-'l -530 47 G64 1 8 -416 -CO 521 356 -..11 -483 K— 1 2 3 4 5 262 490 20 1 2Cl -65 196 228 -487 -2CS lt>9 -oO 19LJ

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228 3 4 5 6 -1'. -1 J -I? 1 1 -10 -o -8 -7 -t> -'o -A -3 -2 1 M = 1 ? 3 A 5 O -J t 1 A 1 3 -12 I 1 -10 -9 -8 -7 -6 -0 -< -3 -2 -1 H = FO I I I VO 30^ -h7 101 -ao 20B -ts 13U 3;.'0 ?4«y 273 37 1 106 10, K1 ? 3 A 'J, -16 -lb lA -13 12 -I 1 -10 -s -e -7 -6 -b -4 -3 -2 -1 336 -6* IVb 293 1 VI 3C.tJ lb2 -6« -67 -C.6 2a 1 133 94 21 6 lt.C 260 1^7 1 09 -66 bC9 -66 320 1 0, K: 2 74 1 16 309 27 9 360 2b3 -66 -66 178 -6b 34b -65 2b7 ~64 -65 -64 23ti -66 b0 2 1 1 2 J 2 PC • i:.o 14Q 31 3 -VO 7 9 1.5 -ro I 160 ri9 I'iO -104 -323 4 1 26? 26;^ -39 £> R 6 IVAi -A -3?f. v3 196 298 -U b 374 14C -30 -1X3 -12 2H6 124 ~':-2 -235 130 24", 1 1 'i 20 6 5 517 6 9 -310 -3 273 1 1 4 -3! 5 -27 3 374 274 -35 35 187 44 -330 -04 246 194 1 A -7 4 I 21 3 — 44 -435 1 25 19 2 10. K = I 2 3 4 •16 15 186 133 262 -69 IbV 142 -66 -20 I 1 01 2^5 81 -205 112 94 •I 4 -1 3 12 -1 1 -1 -Q -3 -7 -6 -5 -4 -3 -2 -1 FO -67 -61. 1 72 -t-J 161 -64 95 227 134 120 108 1 1 I 97 -64 FC -17 • 5 3 1U2 17 -205 -b4 8b 2~^0 14 1 -131 -i;'3 106 106 -4U H= 10. K = 1 1 2 3 -t 7 -16 •1 5 -14 -13 -12 -I 1 -10 -9 -8 -7 -6 -5 -4 -3 H= -15 -14 -1 T -12 -1 I -10 -9 -8 -7 -6 -5 -4 -3 -2 32.5 245 2 59 247 -6 b 22 1 267 167 148 2 y t-C.3 1 4o 1 2ci -64 32 b 297 2:<3 109 2d 1 91 337 242 -266 24 9 -16 -208 -282 176 164 266 -64 140 1 1 1 -26 -326 -301 220 I 10 121 -267 -4 1 1 K = -1 5 -14 -1 3 -1? -1 1 -1 -9 -R -7 -6 -5 -4 H-15 -14 -t 3 -12 -1 I 104 2Cd -CO 169 1 4 9 1 1 7 2 55 -65 277 -66 127 100 130 131 11. K -6 6 -67 -66 1 1 5 26J 22 257 -67 l-jl -or 1 30 1 12 -86 -ins 54 176 l'<7 -127 -276 17 275 94 -112 -140 129 150 28 74 -29 -152 -254 220 239 -85 -182 -56 146 144 1 1 K = 1 3 4 ICO 1 1 1 6 9 ^4 3 •136 I ! 4 -113 1 43 222 I. 10 -'> -H -7 -C \ • -13 12 1 1 10 -9 H-FO 1 89 140 1 04 202 -69 1 1 K = I 75 192 233 1 5-; 1 V7 1 1 K 16U H11. K= 1 2 3 -4 -3 ^ r 1 I 2 3 4 -7 -6 -5 -4 -3 T 1 2 3 4 -9 -a -7 -0 -5 -4 -3 2 1 Z->7 -1,1 220 -69 293 -V J 340 140 124 FC U 8 119 109 198 6 1 169 ; 15 -116 153 1S6 1 1 18^ -10 -269 -31 332 7C -263 -2 31 1 147 -141 2 1 FO 1 03 2 35 H= M 263 -06 2i)H -66 220 255 -69 199 147 254 ie2 140 H= 1 1 28 7 -68 203 tb 161 1 44 171 123 196 152 1 19 30 7 101 214 250 3 •3 04 2 5 208 -244 IOC 192 -lit. -255 193 143 K-8 287 102 213 -35 • 152 -133 190 1 lo 194 -147 1 1 7 302 117 -2C4 M1 1 1 2 3 4 -1 1 -10 -9 -8 -7 -6 -S -4 -3 35^^ 148 22Z 159 -70 -69 143 216 266 216 121 126 -es 119 35 C -147 -233 1J7 a 1 -9 1 13U 203 -273 -21 6 90 124 -1 1 143 h= 1 I . K1 2 3 4 -J 2 1 1 -1 C -9 -8 -7 -6 -5 -4 -3 _ -^ -1 H1 2 3 -13 -12 -1 1 -10 -9 -y -7 6 -5 -4 -3 -2 1 3 < ' 6 -66 132 222 -70 131 IS'* r0 2 1 C4 ir.t) 198 127 -65 13b -67 134 2 4 5 n . K 264 134 -6
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229 f-o FC f-O FC FO FC FO FC — 5

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233 51. D. L. McFadden and A. T. McPhail, J. Cheni. Soc . , Dal ton Trans., 363 (1974) . 52. L. P. Battagla, A. B. Corrandi , C. Palmieri , M. Nardelli, and M. E. V. Tani, Acta Crystallogr , , B3_0, 1114 (1974) . 53. R. F. Chen and J. C. Kernohan , J. Biol. Chera. , 242 5813 (1967) . 54. C. K. Johnson, ORTEP , Report ORNL-379 4 Revised, Oak Ridge National Laboratory, Oak Ridge, Tennessee, 1965. 55. K. Bowman, A. P. Goughan, and Z. Dori, J. Am. Chem. Soc, ^, 727 (1972) . 56. L. E. Godycki and R. E. Rundel, Acta Crystallogr., 6_, 487 (1953) . 57. A, Vaciago and L. Zambonelli, J. Chem. Soc. A, 218 (1970) o 58. The orthogonal coordinates XYZ (in A) are related to the monoclinic fractional coordinates, xyz , by the transformations: X = ax + cz cos3; Y = by; and Z = cz sinB. o 59. The orthogonal coordinates XYZ (in A) are related to the triclinic fractional coordinates, xyz, by the transformations: X = ax + by cosy + cz cosB; Y = by siny cz singcosa*; and Z = cz sinBsina*. 60. D. W. J. Cruickshank and A. P. Robertson, Acta Crystallogr. , 6_, 69S (1953) . 61. M. Calligaris, J. Chem. Soc, Dalton Trans., 1623 (1974). 62. James E. Huheey, "Inorganic Chemistry," Harper and Row, New York, 197 2, p 4 97. 63. Linus Pauling, "The Nature of the Chemical Bond," 3rd ed., Cornell Univ. Press, Ithaca, N. Y., 1960, p 235. 64. T. G. Appleton, H. C. Clark, and L. E. Manzer, Coord. Chem. Revs., 10, 335 (1973). 65. P. G. Stecher, Ed., "Merck Index," 8 th ed . , Merck and Co., Inc., Rahway, N. J., 1963, p 998. 66. D. D. Perrin, Ed., "Dissociation Constants of Organic Bases in Aqueous Solution: Supplement 197 2," Butterworth and Co., Ltd., London, 1972.

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BIOGRAPHICAL SKETCH Douglas Allen Sullivan was born November 9, 1945, in Huntington, West Virginia. In May, 1963, he was graduated from Vinson High School, Huntington, West Virginia. He received the. degree of Bachelor of Science in Chemistry from Marshall University in May, 1967. After studying at the University of Florida from September, 1967, to August, 1968, Mr. Sullivan taught chemistry, physics, physical science, and mathematics for the Wayne County (West Virginia) Board of Education. He then returned to the University of Florida in September, 1972, and received a Master of Science in Teaching degree majoring in chemistry in December, 1974. He is a men\ber of the American Chemical Society. Mr. Sullivan is married to the former Jeanie Delaine Puckett of Titusville, Florida. They have a three-year-old son, David 0' Donald Sullivan. 237

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I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy. Gus J. Palenik, Chairman Professor of Chemistry I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy. '^^^C^/i-L^ R. Carl Stoufer Associate Professor d\ Chemistry I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy. George E. ^yschkewitsch Professor of Chemistry

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I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy. John F. Helling (^ Associate Professor of Chemistry I certify that I have read this study and that in my opinion it conforms to acceptable standards of scholarly presentation and is fully adequate, in scope and quality, as a dissertation for the degree of Doctor of Philosophy. Richard R. Renner Professor of Education This dissertation was submitted to the Graduate Faculty of the Department of Chemistry in the College of Arts and Sciences and to the Graduate Council, and was was accepted as partial fulfillment of the requirements for the degree of Doctor of Philosophy. December, 197 5 Dean, Graduate School

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